Sulfoxide-coontrolled S(N)2' displacements between cyanocuprates and epoxy vinyl sulfoxides

Journal of Organic Chemistry

Volumn 65, Issue 20, 2000, Pages 6462-6473

  Marino, Joseph P ^a   Anna, Laura J ^a   De La Pradilla, Roberto Fernández ^b   Martínez, Maria Victoria ^b   Montero, Carlos ^b   Viso, Alma ^c  

^a UNIVERSITY OF MICHIGAN   (United States)

^b INSTITUTO DE QUÍMICA ORGÁNICA GENERAL   (Spain)

^c UNIVERSIDAD COMPLUTENSE DE MADRID   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

CARBON; COPPER DERIVATIVE; EPOXIDE; EPOXY VINYL SULFOXIDE; LITHIUM; SULFOXIDE; SULFUR; UNCLASSIFIED DRUG; COPPER; ORGANOMETALLIC COMPOUND; SULFONE; VINYL DERIVATIVE;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL BINDING; CHEMICAL MODIFICATION; CHEMICAL STRUCTURE; CHIRALITY; CONFORMATION; DIASTEREOISOMER; ENANTIOMER; METHODOLOGY; REACTION ANALYSIS; STEREOCHEMISTRY; STRUCTURE ANALYSIS; SYNTHESIS; CHEMISTRY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; STEREOISOMERISM;

COPPER; EPOXY COMPOUNDS; MAGNETIC RESONANCE SPECTROSCOPY; ORGANOMETALLIC COMPOUNDS; STEREOISOMERISM; SULFONES; SULFOXIDES; VINYL COMPOUNDS;

EID: 0034612880     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo000468k     Document Type: Article

References (134)

1. Taken in part from the M.S. Thesis of M. V. M.; Ph. D. Theses of C. M. and L. J. A. For a preliminary report, see: Marino, J. P.; Anna, L. J.; Fernández de la Pradilla, R.; Martínez, M. V.; Montero, C.; Viso, A. Tetrahedron Lett. 1996, 37, 8031-8034.
2. For leading reviews in acyclic stereocontrol, see: (a) Oare, D. A.; Heathcock, C. H. In Topics in Stereochemistry; Eliel, E. L., Wilen, S. H., Eds.; Wiley: New York, 1989; Vol. 19, pp 227-407. (b) Evans, D. A.; Nelson, J. V.; Taber, T. R. In Topics in Stereochemistry; Allinger, N. L., Eliel, E. L., Wilen, S. H., Eds.; Wiley: New York, 1982; Vol. 13, pp 1-115. (c) Mukaiyama, T.; Kobayashi, S. Org. React. 1994, 46, 1-103. (d) Nakai, T.; Mikami, K. Org. React. 1994, 46, 105-209. (e) Bartlett, P. A. Tetrahedron 1981, 36, 3-72. (f) Nogradi, N. Stereoselective Synthesis; VCH: Weinheim, Germany, 1995. (g) Cox, L. R.; Ley, S. V. Chem. Soc. Rev. 1998, 27, 301-314. (h) Cha, J. K.; Kim, N.-S. Chem. Rev. 1995, 96, 1761-1795.
3. For leading reviews in acyclic stereocontrol, see: (a) Oare, D. A.; Heathcock, C. H. In Topics in Stereochemistry; Eliel, E. L., Wilen, S. H., Eds.; Wiley: New York, 1989; Vol. 19, pp 227-407. (b) Evans, D. A.; Nelson, J. V.; Taber, T. R. In Topics in Stereochemistry; Allinger, N. L., Eliel, E. L., Wilen, S. H., Eds.; Wiley: New York, 1982; Vol. 13, pp 1-115. (c) Mukaiyama, T.; Kobayashi, S. Org. React. 1994, 46, 1-103. (d) Nakai, T.; Mikami, K. Org. React. 1994, 46, 105-209. (e) Bartlett, P. A. Tetrahedron 1981, 36, 3-72. (f) Nogradi, N. Stereoselective Synthesis; VCH: Weinheim, Germany, 1995. (g) Cox, L. R.; Ley, S. V. Chem. Soc. Rev. 1998, 27, 301-314. (h) Cha, J. K.; Kim, N.-S. Chem. Rev. 1995, 96, 1761-1795.
4. For leading reviews in acyclic stereocontrol, see: (a) Oare, D. A.; Heathcock, C. H. In Topics in Stereochemistry; Eliel, E. L., Wilen, S. H., Eds.; Wiley: New York, 1989; Vol. 19, pp 227-407. (b) Evans, D. A.; Nelson, J. V.; Taber, T. R. In Topics in Stereochemistry; Allinger, N. L., Eliel, E. L., Wilen, S. H., Eds.; Wiley: New York, 1982; Vol. 13, pp 1-115. (c) Mukaiyama, T.; Kobayashi, S. Org. React. 1994, 46, 1-103. (d) Nakai, T.; Mikami, K. Org. React. 1994, 46, 105-209. (e) Bartlett, P. A. Tetrahedron 1981, 36, 3-72. (f) Nogradi, N. Stereoselective Synthesis; VCH: Weinheim, Germany, 1995. (g) Cox, L. R.; Ley, S. V. Chem. Soc. Rev. 1998, 27, 301-314. (h) Cha, J. K.; Kim, N.-S. Chem. Rev. 1995, 96, 1761-1795.
5. For leading reviews in acyclic stereocontrol, see: (a) Oare, D. A.; Heathcock, C. H. In Topics in Stereochemistry; Eliel, E. L., Wilen, S. H., Eds.; Wiley: New York, 1989; Vol. 19, pp 227-407. (b) Evans, D. A.; Nelson, J. V.; Taber, T. R. In Topics in Stereochemistry; Allinger, N. L., Eliel, E. L., Wilen, S. H., Eds.; Wiley: New York, 1982; Vol. 13, pp 1-115. (c) Mukaiyama, T.; Kobayashi, S. Org. React. 1994, 46, 1-103. (d) Nakai, T.; Mikami, K. Org. React. 1994, 46, 105-209. (e) Bartlett, P. A. Tetrahedron 1981, 36, 3-72. (f) Nogradi, N. Stereoselective Synthesis; VCH: Weinheim, Germany, 1995. (g) Cox, L. R.; Ley, S. V. Chem. Soc. Rev. 1998, 27, 301-314. (h) Cha, J. K.; Kim, N.-S. Chem. Rev. 1995, 96, 1761-1795.
6. For leading reviews in acyclic stereocontrol, see: (a) Oare, D. A.; Heathcock, C. H. In Topics in Stereochemistry; Eliel, E. L., Wilen, S. H., Eds.; Wiley: New York, 1989; Vol. 19, pp 227-407. (b) Evans, D. A.; Nelson, J. V.; Taber, T. R. In Topics in Stereochemistry; Allinger, N. L., Eliel, E. L., Wilen, S. H., Eds.; Wiley: New York, 1982; Vol. 13, pp 1-115. (c) Mukaiyama, T.; Kobayashi, S. Org. React. 1994, 46, 1-103. (d) Nakai, T.; Mikami, K. Org. React. 1994, 46, 105-209. (e) Bartlett, P. A. Tetrahedron 1981, 36, 3-72. (f) Nogradi, N. Stereoselective Synthesis; VCH: Weinheim, Germany, 1995. (g) Cox, L. R.; Ley, S. V. Chem. Soc. Rev. 1998, 27, 301-314. (h) Cha, J. K.; Kim, N.-S. Chem. Rev. 1995, 96, 1761-1795.
7. For leading reviews in acyclic stereocontrol, see: (a) Oare, D. A.; Heathcock, C. H. In Topics in Stereochemistry; Eliel, E. L., Wilen, S. H., Eds.; Wiley: New York, 1989; Vol. 19, pp 227-407. (b) Evans, D. A.; Nelson, J. V.; Taber, T. R. In Topics in Stereochemistry; Allinger, N. L., Eliel, E. L., Wilen, S. H., Eds.; Wiley: New York, 1982; Vol. 13, pp 1-115. (c) Mukaiyama, T.; Kobayashi, S. Org. React. 1994, 46, 1-103. (d) Nakai, T.; Mikami, K. Org. React. 1994, 46, 105-209. (e) Bartlett, P. A. Tetrahedron 1981, 36, 3-72. (f) Nogradi, N. Stereoselective Synthesis; VCH: Weinheim, Germany, 1995. (g) Cox, L. R.; Ley, S. V. Chem. Soc. Rev. 1998, 27, 301-314. (h) Cha, J. K.; Kim, N.-S. Chem. Rev. 1995, 96, 1761-1795.
8. For leading reviews in acyclic stereocontrol, see: (a) Oare, D. A.; Heathcock, C. H. In Topics in Stereochemistry; Eliel, E. L., Wilen, S. H., Eds.; Wiley: New York, 1989; Vol. 19, pp 227-407. (b) Evans, D. A.; Nelson, J. V.; Taber, T. R. In Topics in Stereochemistry; Allinger, N. L., Eliel, E. L., Wilen, S. H., Eds.; Wiley: New York, 1982; Vol. 13, pp 1-115. (c) Mukaiyama, T.; Kobayashi, S. Org. React. 1994, 46, 1-103. (d) Nakai, T.; Mikami, K. Org. React. 1994, 46, 105-209. (e) Bartlett, P. A. Tetrahedron 1981, 36, 3-72. (f) Nogradi, N. Stereoselective Synthesis; VCH: Weinheim, Germany, 1995. (g) Cox, L. R.; Ley, S. V. Chem. Soc. Rev. 1998, 27, 301-314. (h) Cha, J. K.; Kim, N.-S. Chem. Rev. 1995, 96, 1761-1795.
9. For leading reviews in acyclic stereocontrol, see: (a) Oare, D. A.; Heathcock, C. H. In Topics in Stereochemistry; Eliel, E. L., Wilen, S. H., Eds.; Wiley: New York, 1989; Vol. 19, pp 227-407. (b) Evans, D. A.; Nelson, J. V.; Taber, T. R. In Topics in Stereochemistry; Allinger, N. L., Eliel, E. L., Wilen, S. H., Eds.; Wiley: New York, 1982; Vol. 13, pp 1-115. (c) Mukaiyama, T.; Kobayashi, S. Org. React. 1994, 46, 1-103. (d) Nakai, T.; Mikami, K. Org. React. 1994, 46, 105-209. (e) Bartlett, P. A. Tetrahedron 1981, 36, 3-72. (f) Nogradi, N. Stereoselective Synthesis; VCH: Weinheim, Germany, 1995. (g) Cox, L. R.; Ley, S. V. Chem. Soc. Rev. 1998, 27, 301-314. (h) Cha, J. K.; Kim, N.-S. Chem. Rev. 1995, 96, 1761-1795.
10. For reviews on organocopper chemistry, see: (a) Krause, N.; Gerold, N. Angew. Chem., Int. Ed. Engl. 1997, 36, 186-204. (b) Yamamoto, Y. In Methods Organic Chemistry (Houben Weyl), 4th ed.; Helmchen, G., Hoffman, R. W., Mulzer, J., Shauman, E., Eds.; Georg Thieme Verlag, Stuttgart, Germany, 1995; Vol. E21b, pp 2401-2067. (c) Lipshutz, B. H. In Advances in Metal-Organic Chemistry; Liebeskind, L. S., Ed.; JAI Press: Greenwich, CT, 1995; Vol. 4, pp 1-64. (d) Lipshutz, B. H. In Organometallics in Synthesis; Schlosser, M., Ed.; Wiley: Chichester, 1994; pp 283-382. (e) Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117-2188. (f) Wipf, P. Synthesis 1993, 537- 557. (f) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135-631. (g) Kozlowski, J. A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 4, pp 169-198. (h) Lipshutz, B. H. Synlett 1990, 119-128. (i) Lipshutz, B. H. Synthesis 1987, 325-341. (j) Yamamoto, Y. Angew. Chem., Int. Ed. Engl. 1986, 25, 947-959, and references therein.
11. For reviews on organocopper chemistry, see: (a) Krause, N.; Gerold, N. Angew. Chem., Int. Ed. Engl. 1997, 36, 186-204. (b) Yamamoto, Y. In Methods Organic Chemistry (Houben Weyl), 4th ed.; Helmchen, G., Hoffman, R. W., Mulzer, J., Shauman, E., Eds.; Georg Thieme Verlag, Stuttgart, Germany, 1995; Vol. E21b, pp 2401-2067. (c) Lipshutz, B. H. In Advances in Metal-Organic Chemistry; Liebeskind, L. S., Ed.; JAI Press: Greenwich, CT, 1995; Vol. 4, pp 1-64. (d) Lipshutz, B. H. In Organometallics in Synthesis; Schlosser, M., Ed.; Wiley: Chichester, 1994; pp 283-382. (e) Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117-2188. (f) Wipf, P. Synthesis 1993, 537- 557. (f) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135-631. (g) Kozlowski, J. A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 4, pp 169-198. (h) Lipshutz, B. H. Synlett 1990, 119-128. (i) Lipshutz, B. H. Synthesis 1987, 325-341. (j) Yamamoto, Y. Angew. Chem., Int. Ed. Engl. 1986, 25, 947-959, and references therein.
12. For reviews on organocopper chemistry, see: (a) Krause, N.; Gerold, N. Angew. Chem., Int. Ed. Engl. 1997, 36, 186-204. (b) Yamamoto, Y. In Methods Organic Chemistry (Houben Weyl), 4th ed.; Helmchen, G., Hoffman, R. W., Mulzer, J., Shauman, E., Eds.; Georg Thieme Verlag, Stuttgart, Germany, 1995; Vol. E21b, pp 2401-2067. (c) Lipshutz, B. H. In Advances in Metal-Organic Chemistry; Liebeskind, L. S., Ed.; JAI Press: Greenwich, CT, 1995; Vol. 4, pp 1-64. (d) Lipshutz, B. H. In Organometallics in Synthesis; Schlosser, M., Ed.; Wiley: Chichester, 1994; pp 283-382. (e) Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117-2188. (f) Wipf, P. Synthesis 1993, 537- 557. (f) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135-631. (g) Kozlowski, J. A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 4, pp 169-198. (h) Lipshutz, B. H. Synlett 1990, 119-128. (i) Lipshutz, B. H. Synthesis 1987, 325-341. (j) Yamamoto, Y. Angew. Chem., Int. Ed. Engl. 1986, 25, 947-959, and references therein.
13. For reviews on organocopper chemistry, see: (a) Krause, N.; Gerold, N. Angew. Chem., Int. Ed. Engl. 1997, 36, 186-204. (b) Yamamoto, Y. In Methods Organic Chemistry (Houben Weyl), 4th ed.; Helmchen, G., Hoffman, R. W., Mulzer, J., Shauman, E., Eds.; Georg Thieme Verlag, Stuttgart, Germany, 1995; Vol. E21b, pp 2401-2067. (c) Lipshutz, B. H. In Advances in Metal-Organic Chemistry; Liebeskind, L. S., Ed.; JAI Press: Greenwich, CT, 1995; Vol. 4, pp 1-64. (d) Lipshutz, B. H. In Organometallics in Synthesis; Schlosser, M., Ed.; Wiley: Chichester, 1994; pp 283-382. (e) Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117-2188. (f) Wipf, P. Synthesis 1993, 537- 557. (f) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135-631. (g) Kozlowski, J. A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 4, pp 169-198. (h) Lipshutz, B. H. Synlett 1990, 119-128. (i) Lipshutz, B. H. Synthesis 1987, 325-341. (j) Yamamoto, Y. Angew. Chem., Int. Ed. Engl. 1986, 25, 947-959, and references therein.
14. For reviews on organocopper chemistry, see: (a) Krause, N.; Gerold, N. Angew. Chem., Int. Ed. Engl. 1997, 36, 186-204. (b) Yamamoto, Y. In Methods Organic Chemistry (Houben Weyl), 4th ed.; Helmchen, G., Hoffman, R. W., Mulzer, J., Shauman, E., Eds.; Georg Thieme Verlag, Stuttgart, Germany, 1995; Vol. E21b, pp 2401-2067. (c) Lipshutz, B. H. In Advances in Metal-Organic Chemistry; Liebeskind, L. S., Ed.; JAI Press: Greenwich, CT, 1995; Vol. 4, pp 1-64. (d) Lipshutz, B. H. In Organometallics in Synthesis; Schlosser, M., Ed.; Wiley: Chichester, 1994; pp 283-382. (e) Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117-2188. (f) Wipf, P. Synthesis 1993, 537- 557. (f) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135-631. (g) Kozlowski, J. A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 4, pp 169-198. (h) Lipshutz, B. H. Synlett 1990, 119-128. (i) Lipshutz, B. H. Synthesis 1987, 325-341. (j) Yamamoto, Y. Angew. Chem., Int. Ed. Engl. 1986, 25, 947-959, and references therein.
15. For reviews on organocopper chemistry, see: (a) Krause, N.; Gerold, N. Angew. Chem., Int. Ed. Engl. 1997, 36, 186-204. (b) Yamamoto, Y. In Methods Organic Chemistry (Houben Weyl), 4th ed.; Helmchen, G., Hoffman, R. W., Mulzer, J., Shauman, E., Eds.; Georg Thieme Verlag, Stuttgart, Germany, 1995; Vol. E21b, pp 2401-2067. (c) Lipshutz, B. H. In Advances in Metal-Organic Chemistry; Liebeskind, L. S., Ed.; JAI Press: Greenwich, CT, 1995; Vol. 4, pp 1-64. (d) Lipshutz, B. H. In Organometallics in Synthesis; Schlosser, M., Ed.; Wiley: Chichester, 1994; pp 283-382. (e) Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117-2188. (f) Wipf, P. Synthesis 1993, 537-557. (f) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135-631. (g) Kozlowski, J. A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 4, pp 169-198. (h) Lipshutz, B. H. Synlett 1990, 119-128. (i) Lipshutz, B. H. Synthesis 1987, 325-341. (j) Yamamoto, Y. Angew. Chem., Int. Ed. Engl. 1986, 25, 947-959, and references therein.
16. For reviews on organocopper chemistry, see: (a) Krause, N.; Gerold, N. Angew. Chem., Int. Ed. Engl. 1997, 36, 186-204. (b) Yamamoto, Y. In Methods Organic Chemistry (Houben Weyl), 4th ed.; Helmchen, G., Hoffman, R. W., Mulzer, J., Shauman, E., Eds.; Georg Thieme Verlag, Stuttgart, Germany, 1995; Vol. E21b, pp 2401-2067. (c) Lipshutz, B. H. In Advances in Metal-Organic Chemistry; Liebeskind, L. S., Ed.; JAI Press: Greenwich, CT, 1995; Vol. 4, pp 1-64. (d) Lipshutz, B. H. In Organometallics in Synthesis; Schlosser, M., Ed.; Wiley: Chichester, 1994; pp 283-382. (e) Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117-2188. (f) Wipf, P. Synthesis 1993, 537- 557. (f) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135-631. (g) Kozlowski, J. A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 4, pp 169-198. (h) Lipshutz, B. H. Synlett 1990, 119-128. (i) Lipshutz, B. H. Synthesis 1987, 325-341. (j) Yamamoto, Y. Angew. Chem., Int. Ed. Engl. 1986, 25, 947-959, and references therein.
17. For reviews on organocopper chemistry, see: (a) Krause, N.; Gerold, N. Angew. Chem., Int. Ed. Engl. 1997, 36, 186-204. (b) Yamamoto, Y. In Methods Organic Chemistry (Houben Weyl), 4th ed.; Helmchen, G., Hoffman, R. W., Mulzer, J., Shauman, E., Eds.; Georg Thieme Verlag, Stuttgart, Germany, 1995; Vol. E21b, pp 2401-2067. (c) Lipshutz, B. H. In Advances in Metal-Organic Chemistry; Liebeskind, L. S., Ed.; JAI Press: Greenwich, CT, 1995; Vol. 4, pp 1-64. (d) Lipshutz, B. H. In Organometallics in Synthesis; Schlosser, M., Ed.; Wiley: Chichester, 1994; pp 283-382. (e) Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117-2188. (f) Wipf, P. Synthesis 1993, 537- 557. (f) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135-631. (g) Kozlowski, J. A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 4, pp 169-198. (h) Lipshutz, B. H. Synlett 1990, 119-128. (i) Lipshutz, B. H. Synthesis 1987, 325-341. (j) Yamamoto, Y. Angew. Chem., Int. Ed. Engl. 1986, 25, 947-959, and references therein.
18. For reviews on organocopper chemistry, see: (a) Krause, N.; Gerold, N. Angew. Chem., Int. Ed. Engl. 1997, 36, 186-204. (b) Yamamoto, Y. In Methods Organic Chemistry (Houben Weyl), 4th ed.; Helmchen, G., Hoffman, R. W., Mulzer, J., Shauman, E., Eds.; Georg Thieme Verlag, Stuttgart, Germany, 1995; Vol. E21b, pp 2401-2067. (c) Lipshutz, B. H. In Advances in Metal-Organic Chemistry; Liebeskind, L. S., Ed.; JAI Press: Greenwich, CT, 1995; Vol. 4, pp 1-64. (d) Lipshutz, B. H. In Organometallics in Synthesis; Schlosser, M., Ed.; Wiley: Chichester, 1994; pp 283-382. (e) Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117-2188. (f) Wipf, P. Synthesis 1993, 537- 557. (f) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135-631. (g) Kozlowski, J. A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 4, pp 169-198. (h) Lipshutz, B. H. Synlett 1990, 119-128. (i) Lipshutz, B. H. Synthesis 1987, 325-341. (j) Yamamoto, Y. Angew. Chem., Int. Ed. Engl. 1986, 25, 947-959, and references therein.
19. For reviews on organocopper chemistry, see: (a) Krause, N.; Gerold, N. Angew. Chem., Int. Ed. Engl. 1997, 36, 186-204. (b) Yamamoto, Y. In Methods Organic Chemistry (Houben Weyl), 4th ed.; Helmchen, G., Hoffman, R. W., Mulzer, J., Shauman, E., Eds.; Georg Thieme Verlag, Stuttgart, Germany, 1995; Vol. E21b, pp 2401-2067. (c) Lipshutz, B. H. In Advances in Metal-Organic Chemistry; Liebeskind, L. S., Ed.; JAI Press: Greenwich, CT, 1995; Vol. 4, pp 1-64. (d) Lipshutz, B. H. In Organometallics in Synthesis; Schlosser, M., Ed.; Wiley: Chichester, 1994; pp 283-382. (e) Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117-2188. (f) Wipf, P. Synthesis 1993, 537- 557. (f) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135-631. (g) Kozlowski, J. A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 4, pp 169-198. (h) Lipshutz, B. H. Synlett 1990, 119-128. (i) Lipshutz, B. H. Synthesis 1987, 325-341. (j) Yamamoto, Y. Angew. Chem., Int. Ed. Engl. 1986, 25, 947-959, and references therein.
20. For reviews on organocopper chemistry, see: (a) Krause, N.; Gerold, N. Angew. Chem., Int. Ed. Engl. 1997, 36, 186-204. (b) Yamamoto, Y. In Methods Organic Chemistry (Houben Weyl), 4th ed.; Helmchen, G., Hoffman, R. W., Mulzer, J., Shauman, E., Eds.; Georg Thieme Verlag, Stuttgart, Germany, 1995; Vol. E21b, pp 2401-2067. (c) Lipshutz, B. H. In Advances in Metal-Organic Chemistry; Liebeskind, L. S., Ed.; JAI Press: Greenwich, CT, 1995; Vol. 4, pp 1-64. (d) Lipshutz, B. H. In Organometallics in Synthesis; Schlosser, M., Ed.; Wiley: Chichester, 1994; pp 283-382. (e) Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117-2188. (f) Wipf, P. Synthesis 1993, 537- 557. (f) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135-631. (g) Kozlowski, J. A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 4, pp 169-198. (h) Lipshutz, B. H. Synlett 1990, 119-128. (i) Lipshutz, B. H. Synthesis 1987, 325-341. (j) Yamamoto, Y. Angew. Chem., Int. Ed. Engl. 1986, 25, 947-959, and references therein.
21. N2 ′ displacements on vinyl aziridines, see: (j) Toda, A.; Aoyama, H.; Mimura, N.; Ohno, H.; Fujii, N.; Ibuka, T. J. Org. Chem. 1998, 63, 7053-7061. (k) Ibuka, T.; Mimura, N.; Ohno, H.; Nakai, K.; Akaji, M.; Habashita, H.; Tamamura, H.; Miwa, Y.; Taga, T.; Fujii, N.; Yamamoto Y. J. Org. Chem. 1997, 62, 2982-2991. (l) Wipf, P.; Henninger, T. C.; Geib, S, J. J. Org. Chem. 1998, 63, 6088-6089. (m) Wipf, P.; Fritch, P. C. J. Org. Chem. 1994, 59, 4875-4886.
22. N2 ′ displacements on vinyl aziridines, see: (j) Toda, A.; Aoyama, H.; Mimura, N.; Ohno, H.; Fujii, N.; Ibuka, T. J. Org. Chem. 1998, 63, 7053-7061. (k) Ibuka, T.; Mimura, N.; Ohno, H.; Nakai, K.; Akaji, M.; Habashita, H.; Tamamura, H.; Miwa, Y.; Taga, T.; Fujii, N.; Yamamoto Y. J. Org. Chem. 1997, 62, 2982-2991. (l) Wipf, P.; Henninger, T. C.; Geib, S, J. J. Org. Chem. 1998, 63, 6088-6089. (m) Wipf, P.; Fritch, P. C. J. Org. Chem. 1994, 59, 4875-4886.
23. N2 ′ displacements on vinyl aziridines, see: (j) Toda, A.; Aoyama, H.; Mimura, N.; Ohno, H.; Fujii, N.; Ibuka, T. J. Org. Chem. 1998, 63, 7053-7061. (k) Ibuka, T.; Mimura, N.; Ohno, H.; Nakai, K.; Akaji, M.; Habashita, H.; Tamamura, H.; Miwa, Y.; Taga, T.; Fujii, N.; Yamamoto Y. J. Org. Chem. 1997, 62, 2982-2991. (l) Wipf, P.; Henninger, T. C.; Geib, S, J. J. Org. Chem. 1998, 63, 6088-6089. (m) Wipf, P.; Fritch, P. C. J. Org. Chem. 1994, 59, 4875-4886.
24. N2 ′ displacements on vinyl aziridines, see: (j) Toda, A.; Aoyama, H.; Mimura, N.; Ohno, H.; Fujii, N.; Ibuka, T. J. Org. Chem. 1998, 63, 7053-7061. (k) Ibuka, T.; Mimura, N.; Ohno, H.; Nakai, K.; Akaji, M.; Habashita, H.; Tamamura, H.; Miwa, Y.; Taga, T.; Fujii, N.; Yamamoto Y. J. Org. Chem. 1997, 62, 2982-2991. (l) Wipf, P.; Henninger, T. C.; Geib, S, J. J. Org. Chem. 1998, 63, 6088-6089. (m) Wipf, P.; Fritch, P. C. J. Org. Chem. 1994, 59, 4875-4886.
25. N2 ′ displacements on vinyl aziridines, see: (j) Toda, A.; Aoyama, H.; Mimura, N.; Ohno, H.; Fujii, N.; Ibuka, T. J. Org. Chem. 1998, 63, 7053-7061. (k) Ibuka, T.; Mimura, N.; Ohno, H.; Nakai, K.; Akaji, M.; Habashita, H.; Tamamura, H.; Miwa, Y.; Taga, T.; Fujii, N.; Yamamoto Y. J. Org. Chem. 1997, 62, 2982-2991. (l) Wipf, P.; Henninger, T. C.; Geib, S, J. J. Org. Chem. 1998, 63, 6088-6089. (m) Wipf, P.; Fritch, P. C. J. Org. Chem. 1994, 59, 4875-4886.
26. N2 ′ displacements on vinyl aziridines, see: (j) Toda, A.; Aoyama, H.; Mimura, N.; Ohno, H.; Fujii, N.; Ibuka, T. J. Org. Chem. 1998, 63, 7053-7061. (k) Ibuka, T.; Mimura, N.; Ohno, H.; Nakai, K.; Akaji, M.; Habashita, H.; Tamamura, H.; Miwa, Y.; Taga, T.; Fujii, N.; Yamamoto Y. J. Org. Chem. 1997, 62, 2982-2991. (l) Wipf, P.; Henninger, T. C.; Geib, S, J. J. Org. Chem. 1998, 63, 6088-6089. (m) Wipf, P.; Fritch, P. C. J. Org. Chem. 1994, 59, 4875-4886.
27. N2 ′ displacements on vinyl aziridines, see: (j) Toda, A.; Aoyama, H.; Mimura, N.; Ohno, H.; Fujii, N.; Ibuka, T. J. Org. Chem. 1998, 63, 7053-7061. (k) Ibuka, T.; Mimura, N.; Ohno, H.; Nakai, K.; Akaji, M.; Habashita, H.; Tamamura, H.; Miwa, Y.; Taga, T.; Fujii, N.; Yamamoto Y. J. Org. Chem. 1997, 62, 2982-2991. (l) Wipf, P.; Henninger, T. C.; Geib, S, J. J. Org. Chem. 1998, 63, 6088-6089. (m) Wipf, P.; Fritch, P. C. J. Org. Chem. 1994, 59, 4875-4886.
28. N2 ′ displacements on vinyl aziridines, see: (j) Toda, A.; Aoyama, H.; Mimura, N.; Ohno, H.; Fujii, N.; Ibuka, T. J. Org. Chem. 1998, 63, 7053-7061. (k) Ibuka, T.; Mimura, N.; Ohno, H.; Nakai, K.; Akaji, M.; Habashita, H.; Tamamura, H.; Miwa, Y.; Taga, T.; Fujii, N.; Yamamoto Y. J. Org. Chem. 1997, 62, 2982-2991. (l) Wipf, P.; Henninger, T. C.; Geib, S, J. J. Org. Chem. 1998, 63, 6088-6089. (m) Wipf, P.; Fritch, P. C. J. Org. Chem. 1994, 59, 4875-4886.
29. N2 ′ displacements on vinyl aziridines, see: (j) Toda, A.; Aoyama, H.; Mimura, N.; Ohno, H.; Fujii, N.; Ibuka, T. J. Org. Chem. 1998, 63, 7053-7061. (k) Ibuka, T.; Mimura, N.; Ohno, H.; Nakai, K.; Akaji, M.; Habashita, H.; Tamamura, H.; Miwa, Y.; Taga, T.; Fujii, N.; Yamamoto Y. J. Org. Chem. 1997, 62, 2982-2991. (l) Wipf, P.; Henninger, T. C.; Geib, S, J. J. Org. Chem. 1998, 63, 6088-6089. (m) Wipf, P.; Fritch, P. C. J. Org. Chem. 1994, 59, 4875-4886.
30. N2 ′ displacements on vinyl aziridines, see: (j) Toda, A.; Aoyama, H.; Mimura, N.; Ohno, H.; Fujii, N.; Ibuka, T. J. Org. Chem. 1998, 63, 7053-7061. (k) Ibuka, T.; Mimura, N.; Ohno, H.; Nakai, K.; Akaji, M.; Habashita, H.; Tamamura, H.; Miwa, Y.; Taga, T.; Fujii, N.; Yamamoto Y. J. Org. Chem. 1997, 62, 2982-2991. (l) Wipf, P.; Henninger, T. C.; Geib, S, J. J. Org. Chem. 1998, 63, 6088-6089. (m) Wipf, P.; Fritch, P. C. J. Org. Chem. 1994, 59, 4875-4886.
31. N2 ′ displacements on vinyl aziridines, see: (j) Toda, A.; Aoyama, H.; Mimura, N.; Ohno, H.; Fujii, N.; Ibuka, T. J. Org. Chem. 1998, 63, 7053-7061. (k) Ibuka, T.; Mimura, N.; Ohno, H.; Nakai, K.; Akaji, M.; Habashita, H.; Tamamura, H.; Miwa, Y.; Taga, T.; Fujii, N.; Yamamoto Y. J. Org. Chem. 1997, 62, 2982-2991. (l) Wipf, P.; Henninger, T. C.; Geib, S, J. J. Org. Chem. 1998, 63, 6088-6089. (m) Wipf, P.; Fritch, P. C. J. Org. Chem. 1994, 59, 4875-4886.
32. N2 ′ displacements on vinyl aziridines, see: (j) Toda, A.; Aoyama, H.; Mimura, N.; Ohno, H.; Fujii, N.; Ibuka, T. J. Org. Chem. 1998, 63, 7053-7061. (k) Ibuka, T.; Mimura, N.; Ohno, H.; Nakai, K.; Akaji, M.; Habashita, H.; Tamamura, H.; Miwa, Y.; Taga, T.; Fujii, N.; Yamamoto Y. J. Org. Chem. 1997, 62, 2982-2991. (l) Wipf, P.; Henninger, T. C.; Geib, S, J. J. Org. Chem. 1998, 63, 6088-6089. (m) Wipf, P.; Fritch, P. C. J. Org. Chem. 1994, 59, 4875-4886.
33. N2 ′ displacements on vinyl aziridines, see: (j) Toda, A.; Aoyama, H.; Mimura, N.; Ohno, H.; Fujii, N.; Ibuka, T. J. Org. Chem. 1998, 63, 7053-7061. (k) Ibuka, T.; Mimura, N.; Ohno, H.; Nakai, K.; Akaji, M.; Habashita, H.; Tamamura, H.; Miwa, Y.; Taga, T.; Fujii, N.; Yamamoto Y. J. Org. Chem. 1997, 62, 2982-2991. (l) Wipf, P.; Henninger, T. C.; Geib, S, J. J. Org. Chem. 1998, 63, 6088-6089. (m) Wipf, P.; Fritch, P. C. J. Org. Chem. 1994, 59, 4875-4886.
34. (a) Marino, J. P.; Viso, A.; Lee, J.-D.; Fernández de la Pradilla, R.; Fernández, P.; Rubio, M. B. J. Org. Chem. 1997, 62, 645-653.
35. (b) Marino, J. P.; Viso, A.; Fernández de la Pradilla, R.; Fernández, P. J. Org. Chem. 1991, 56, 1349-1351.
36. For reviews on synthetic applications of sulfoxides, see: (a) Carreno, M. C. Chem. Rev. 1995, 95, 1717-1760. (b) Walker, A. J. Tetrahedron: Asymmetry 1992, 3, 961-968. (c) García Ruano, J. L.; Cid de la Plata, B. Top. Curr. Chem. 1999, 204, 1-126. (d) Procter, D. J. J. Chem. Soc., Perkin Trans. 1 1999, 641-667. (e) Allin, S. M.; Page, P. C. B. Org. Prep. Proc. Int. 1998, 30, 145-176. (f) Padwa, A.; Gunn, D. E., Jr.; Osterhout, M. H. Synthesis 1997, 1353-1377. (g) Marino, J. P. Pure Appl. Chem. 1993, 65, 667-674. For leading references on applications of vinyl sulfoxides, see: (h) Fernández de la Pradilla, R.; Castro, S.; Manzano, P.; Martin-Ortega, M.; Priego, J.; Viso, A.; Rodriguez, A.; Fonseca, I. J. Org. Chem. 1998, 63, 4954-4966. (i) Adrio, J.; Carretero, J. C. J. Am. Chem. Soc. 1999, 121, 7411-7412. (j) Priego, J.; Carretero, J. C. Synlett 1999, 1603-1605. (k) Delouvrié, B.; Fensterbank, L.; Lacôte, E.; Malacria, M. J. Am. Chem. Soc. 1999, 121, 11395-11401.
37. For reviews on synthetic applications of sulfoxides, see: (a) Carreno, M. C. Chem. Rev. 1995, 95, 1717-1760. (b) Walker, A. J. Tetrahedron: Asymmetry 1992, 3, 961-968. (c) García Ruano, J. L.; Cid de la Plata, B. Top. Curr. Chem. 1999, 204, 1-126. (d) Procter, D. J. J. Chem. Soc., Perkin Trans. 1 1999, 641-667. (e) Allin, S. M.; Page, P. C. B. Org. Prep. Proc. Int. 1998, 30, 145-176. (f) Padwa, A.; Gunn, D. E., Jr.; Osterhout, M. H. Synthesis 1997, 1353-1377. (g) Marino, J. P. Pure Appl. Chem. 1993, 65, 667-674. For leading references on applications of vinyl sulfoxides, see: (h) Fernández de la Pradilla, R.; Castro, S.; Manzano, P.; Martin-Ortega, M.; Priego, J.; Viso, A.; Rodriguez, A.; Fonseca, I. J. Org. Chem. 1998, 63, 4954-4966. (i) Adrio, J.; Carretero, J. C. J. Am. Chem. Soc. 1999, 121, 7411-7412. (j) Priego, J.; Carretero, J. C. Synlett 1999, 1603-1605. (k) Delouvrié, B.; Fensterbank, L.; Lacôte, E.; Malacria, M. J. Am. Chem. Soc. 1999, 121, 11395-11401.
38. For reviews on synthetic applications of sulfoxides, see: (a) Carreno, M. C. Chem. Rev. 1995, 95, 1717-1760. (b) Walker, A. J. Tetrahedron: Asymmetry 1992, 3, 961-968. (c) García Ruano, J. L.; Cid de la Plata, B. Top. Curr. Chem. 1999, 204, 1-126. (d) Procter, D. J. J. Chem. Soc., Perkin Trans. 1 1999, 641-667. (e) Allin, S. M.; Page, P. C. B. Org. Prep. Proc. Int. 1998, 30, 145-176. (f) Padwa, A.; Gunn, D. E., Jr.; Osterhout, M. H. Synthesis 1997, 1353-1377. (g) Marino, J. P. Pure Appl. Chem. 1993, 65, 667-674. For leading references on applications of vinyl sulfoxides, see: (h) Fernández de la Pradilla, R.; Castro, S.; Manzano, P.; Martin-Ortega, M.; Priego, J.; Viso, A.; Rodriguez, A.; Fonseca, I. J. Org. Chem. 1998, 63, 4954-4966. (i) Adrio, J.; Carretero, J. C. J. Am. Chem. Soc. 1999, 121, 7411-7412. (j) Priego, J.; Carretero, J. C. Synlett 1999, 1603-1605. (k) Delouvrié, B.; Fensterbank, L.; Lacôte, E.; Malacria, M. J. Am. Chem. Soc. 1999, 121, 11395-11401.
39. For reviews on synthetic applications of sulfoxides, see: (a) Carreno, M. C. Chem. Rev. 1995, 95, 1717-1760. (b) Walker, A. J. Tetrahedron: Asymmetry 1992, 3, 961-968. (c) García Ruano, J. L.; Cid de la Plata, B. Top. Curr. Chem. 1999, 204, 1-126. (d) Procter, D. J. J. Chem. Soc., Perkin Trans. 1 1999, 641-667. (e) Allin, S. M.; Page, P. C. B. Org. Prep. Proc. Int. 1998, 30, 145-176. (f) Padwa, A.; Gunn, D. E., Jr.; Osterhout, M. H. Synthesis 1997, 1353-1377. (g) Marino, J. P. Pure Appl. Chem. 1993, 65, 667-674. For leading references on applications of vinyl sulfoxides, see: (h) Fernández de la Pradilla, R.; Castro, S.; Manzano, P.; Martin-Ortega, M.; Priego, J.; Viso, A.; Rodriguez, A.; Fonseca, I. J. Org. Chem. 1998, 63, 4954-4966. (i) Adrio, J.; Carretero, J. C. J. Am. Chem. Soc. 1999, 121, 7411-7412. (j) Priego, J.; Carretero, J. C. Synlett 1999, 1603-1605. (k) Delouvrié, B.; Fensterbank, L.; Lacôte, E.; Malacria, M. J. Am. Chem. Soc. 1999, 121, 11395-11401.
40. For reviews on synthetic applications of sulfoxides, see: (a) Carreno, M. C. Chem. Rev. 1995, 95, 1717-1760. (b) Walker, A. J. Tetrahedron: Asymmetry 1992, 3, 961-968. (c) García Ruano, J. L.; Cid de la Plata, B. Top. Curr. Chem. 1999, 204, 1-126. (d) Procter, D. J. J. Chem. Soc., Perkin Trans. 1 1999, 641-667. (e) Allin, S. M.; Page, P. C. B. Org. Prep. Proc. Int. 1998, 30, 145-176. (f) Padwa, A.; Gunn, D. E., Jr.; Osterhout, M. H. Synthesis 1997, 1353-1377. (g) Marino, J. P. Pure Appl. Chem. 1993, 65, 667-674. For leading references on applications of vinyl sulfoxides, see: (h) Fernández de la Pradilla, R.; Castro, S.; Manzano, P.; Martin-Ortega, M.; Priego, J.; Viso, A.; Rodriguez, A.; Fonseca, I. J. Org. Chem. 1998, 63, 4954-4966. (i) Adrio, J.; Carretero, J. C. J. Am. Chem. Soc. 1999, 121, 7411-7412. (j) Priego, J.; Carretero, J. C. Synlett 1999, 1603-1605. (k) Delouvrié, B.; Fensterbank, L.; Lacôte, E.; Malacria, M. J. Am. Chem. Soc. 1999, 121, 11395-11401.
41. For reviews on synthetic applications of sulfoxides, see: (a) Carreno, M. C. Chem. Rev. 1995, 95, 1717-1760. (b) Walker, A. J. Tetrahedron: Asymmetry 1992, 3, 961-968. (c) García Ruano, J. L.; Cid de la Plata, B. Top. Curr. Chem. 1999, 204, 1-126. (d) Procter, D. J. J. Chem. Soc., Perkin Trans. 1 1999, 641-667. (e) Allin, S. M.; Page, P. C. B. Org. Prep. Proc. Int. 1998, 30, 145-176. (f) Padwa, A.; Gunn, D. E., Jr.; Osterhout, M. H. Synthesis 1997, 1353-1377. (g) Marino, J. P. Pure Appl. Chem. 1993, 65, 667-674. For leading references on applications of vinyl sulfoxides, see: (h) Fernández de la Pradilla, R.; Castro, S.; Manzano, P.; Martin-Ortega, M.; Priego, J.; Viso, A.; Rodriguez, A.; Fonseca, I. J. Org. Chem. 1998, 63, 4954-4966. (i) Adrio, J.; Carretero, J. C. J. Am. Chem. Soc. 1999, 121, 7411-7412. (j) Priego, J.; Carretero, J. C. Synlett 1999, 1603-1605. (k) Delouvrié, B.; Fensterbank, L.; Lacôte, E.; Malacria, M. J. Am. Chem. Soc. 1999, 121, 11395-11401.
42. For reviews on synthetic applications of sulfoxides, see: (a) Carreno, M. C. Chem. Rev. 1995, 95, 1717-1760. (b) Walker, A. J. Tetrahedron: Asymmetry 1992, 3, 961-968. (c) García Ruano, J. L.; Cid de la Plata, B. Top. Curr. Chem. 1999, 204, 1-126. (d) Procter, D. J. J. Chem. Soc., Perkin Trans. 1 1999, 641-667. (e) Allin, S. M.; Page, P. C. B. Org. Prep. Proc. Int. 1998, 30, 145-176. (f) Padwa, A.; Gunn, D. E., Jr.; Osterhout, M. H. Synthesis 1997, 1353-1377. (g) Marino, J. P. Pure Appl. Chem. 1993, 65, 667-674. For leading references on applications of vinyl sulfoxides, see: (h) Fernández de la Pradilla, R.; Castro, S.; Manzano, P.; Martin-Ortega, M.; Priego, J.; Viso, A.; Rodriguez, A.; Fonseca, I. J. Org. Chem. 1998, 63, 4954-4966. (i) Adrio, J.; Carretero, J. C. J. Am. Chem. Soc. 1999, 121, 7411-7412. (j) Priego, J.; Carretero, J. C. Synlett 1999, 1603-1605. (k) Delouvrié, B.; Fensterbank, L.; Lacôte, E.; Malacria, M. J. Am. Chem. Soc. 1999, 121, 11395-11401.
43. For reviews on synthetic applications of sulfoxides, see: (a) Carreno, M. C. Chem. Rev. 1995, 95, 1717-1760. (b) Walker, A. J. Tetrahedron: Asymmetry 1992, 3, 961-968. (c) García Ruano, J. L.; Cid de la Plata, B. Top. Curr. Chem. 1999, 204, 1-126. (d) Procter, D. J. J. Chem. Soc., Perkin Trans. 1 1999, 641-667. (e) Allin, S. M.; Page, P. C. B. Org. Prep. Proc. Int. 1998, 30, 145-176. (f) Padwa, A.; Gunn, D. E., Jr.; Osterhout, M. H. Synthesis 1997, 1353-1377. (g) Marino, J. P. Pure Appl. Chem. 1993, 65, 667-674. For leading references on applications of vinyl sulfoxides, see: (h) Fernández de la Pradilla, R.; Castro, S.; Manzano, P.; Martin-Ortega, M.; Priego, J.; Viso, A.; Rodriguez, A.; Fonseca, I. J. Org. Chem. 1998, 63, 4954-4966. (i) Adrio, J.; Carretero, J. C. J. Am. Chem. Soc. 1999, 121, 7411-7412. (j) Priego, J.; Carretero, J. C. Synlett 1999, 1603-1605. (k) Delouvrié, B.; Fensterbank, L.; Lacôte, E.; Malacria, M. J. Am. Chem. Soc. 1999, 121, 11395-11401.
44. For reviews on synthetic applications of sulfoxides, see: (a) Carreno, M. C. Chem. Rev. 1995, 95, 1717-1760. (b) Walker, A. J. Tetrahedron: Asymmetry 1992, 3, 961-968. (c) García Ruano, J. L.; Cid de la Plata, B. Top. Curr. Chem. 1999, 204, 1-126. (d) Procter, D. J. J. Chem. Soc., Perkin Trans. 1 1999, 641-667. (e) Allin, S. M.; Page, P. C. B. Org. Prep. Proc. Int. 1998, 30, 145-176. (f) Padwa, A.; Gunn, D. E., Jr.; Osterhout, M. H. Synthesis 1997, 1353-1377. (g) Marino, J. P. Pure Appl. Chem. 1993, 65, 667-674. For leading references on applications of vinyl sulfoxides, see: (h) Fernández de la Pradilla, R.; Castro, S.; Manzano, P.; Martin-Ortega, M.; Priego, J.; Viso, A.; Rodriguez, A.; Fonseca, I. J. Org. Chem. 1998, 63, 4954-4966. (i) Adrio, J.; Carretero, J. C. J. Am. Chem. Soc. 1999, 121, 7411-7412. (j) Priego, J.; Carretero, J. C. Synlett 1999, 1603-1605. (k) Delouvrié, B.; Fensterbank, L.; Lacôte, E.; Malacria, M. J. Am. Chem. Soc. 1999, 121, 11395-11401.
45. For reviews on synthetic applications of sulfoxides, see: (a) Carreno, M. C. Chem. Rev. 1995, 95, 1717-1760. (b) Walker, A. J. Tetrahedron: Asymmetry 1992, 3, 961-968. (c) García Ruano, J. L.; Cid de la Plata, B. Top. Curr. Chem. 1999, 204, 1-126. (d) Procter, D. J. J. Chem. Soc., Perkin Trans. 1 1999, 641-667. (e) Allin, S. M.; Page, P. C. B. Org. Prep. Proc. Int. 1998, 30, 145-176. (f) Padwa, A.; Gunn, D. E., Jr.; Osterhout, M. H. Synthesis 1997, 1353-1377. (g) Marino, J. P. Pure Appl. Chem. 1993, 65, 667-674. For leading references on applications of vinyl sulfoxides, see: (h) Fernández de la Pradilla, R.; Castro, S.; Manzano, P.; Martin-Ortega, M.; Priego, J.; Viso, A.; Rodriguez, A.; Fonseca, I. J. Org. Chem. 1998, 63, 4954-4966. (i) Adrio, J.; Carretero, J. C. J. Am. Chem. Soc. 1999, 121, 7411-7412. (j) Priego, J.; Carretero, J. C. Synlett 1999, 1603-1605. (k) Delouvrié, B.; Fensterbank, L.; Lacôte, E.; Malacria, M. J. Am. Chem. Soc. 1999, 121, 11395-11401.
46. For reviews on synthetic applications of sulfoxides, see: (a) Carreno, M. C. Chem. Rev. 1995, 95, 1717-1760. (b) Walker, A. J. Tetrahedron: Asymmetry 1992, 3, 961-968. (c) García Ruano, J. L.; Cid de la Plata, B. Top. Curr. Chem. 1999, 204, 1-126. (d) Procter, D. J. J. Chem. Soc., Perkin Trans. 1 1999, 641-667. (e) Allin, S. M.; Page, P. C. B. Org. Prep. Proc. Int. 1998, 30, 145-176. (f) Padwa, A.; Gunn, D. E., Jr.; Osterhout, M. H. Synthesis 1997, 1353-1377. (g) Marino, J. P. Pure Appl. Chem. 1993, 65, 667-674. For leading references on applications of vinyl sulfoxides, see: (h) Fernández de la Pradilla, R.; Castro, S.; Manzano, P.; Martin-Ortega, M.; Priego, J.; Viso, A.; Rodriguez, A.; Fonseca, I. J. Org. Chem. 1998, 63, 4954-4966. (i) Adrio, J.; Carretero, J. C. J. Am. Chem. Soc. 1999, 121, 7411-7412. (j) Priego, J.; Carretero, J. C. Synlett 1999, 1603-1605. (k) Delouvrié, B.; Fensterbank, L.; Lacôte, E.; Malacria, M. J. Am. Chem. Soc. 1999, 121, 11395-11401.
47. Vinyl sulfones are versatile synthetic intermediates. For selected reviews, see: (a) Simpkins, N. S. Sulphones in Organic Synthesis; Pergamon Press: Oxford, 1993. (b) Fuchs, P. L.; Braish, T. F. Chem. Rev. 1986, 86, 903-917. For leading references, see: (c) Jackson, R. F. W.; Standen S. P.; Clegg, W. J. Chem. Soc., Perkin Trans. 1 1995, 149-156. (d) Garrido, J. L.; Alonso, I.; Carretero, J. C. J. Org. Chem. 1998, 63, 9406-9413. (e) Carretero, J. C.; Gómez Arrayás, R. J. Org. Chem. 1998, 63, 2993-3005. (f) Back, T. G.; Nakajima, K. J. Org. Chem. 1998, 63, 6566-6571. (g) Caturla, F.; Nájera, C. Tetrahedron 1998, 54, 11255-11270. (h) Adrio, J.; Carretero, J. C. Tetrahedron 1998, 54, 1601-1614. (i) Enders, D.; Müller, S. F.; Raabe, G. Angew. Chem., Int. Ed. Engl. 1999, 38, 195-197. (j) Carretero, J. C.; Gómez Arrayás, R. Synlett 1999, 49-50.
48. Vinyl sulfones are versatile synthetic intermediates. For selected reviews, see: (a) Simpkins, N. S. Sulphones in Organic Synthesis; Pergamon Press: Oxford, 1993. (b) Fuchs, P. L.; Braish, T. F. Chem. Rev. 1986, 86, 903-917. For leading references, see: (c) Jackson, R. F. W.; Standen S. P.; Clegg, W. J. Chem. Soc., Perkin Trans. 1 1995, 149-156. (d) Garrido, J. L.; Alonso, I.; Carretero, J. C. J. Org. Chem. 1998, 63, 9406-9413. (e) Carretero, J. C.; Gómez Arrayás, R. J. Org. Chem. 1998, 63, 2993-3005. (f) Back, T. G.; Nakajima, K. J. Org. Chem. 1998, 63, 6566-6571. (g) Caturla, F.; Nájera, C. Tetrahedron 1998, 54, 11255-11270. (h) Adrio, J.; Carretero, J. C. Tetrahedron 1998, 54, 1601-1614. (i) Enders, D.; Müller, S. F.; Raabe, G. Angew. Chem., Int. Ed. Engl. 1999, 38, 195-197. (j) Carretero, J. C.; Gómez Arrayás, R. Synlett 1999, 49-50.
49. Vinyl sulfones are versatile synthetic intermediates. For selected reviews, see: (a) Simpkins, N. S. Sulphones in Organic Synthesis; Pergamon Press: Oxford, 1993. (b) Fuchs, P. L.; Braish, T. F. Chem. Rev. 1986, 86, 903-917. For leading references, see: (c) Jackson, R. F. W.; Standen S. P.; Clegg, W. J. Chem. Soc., Perkin Trans. 1 1995, 149-156. (d) Garrido, J. L.; Alonso, I.; Carretero, J. C. J. Org. Chem. 1998, 63, 9406-9413. (e) Carretero, J. C.; Gómez Arrayás, R. J. Org. Chem. 1998, 63, 2993-3005. (f) Back, T. G.; Nakajima, K. J. Org. Chem. 1998, 63, 6566-6571. (g) Caturla, F.; Nájera, C. Tetrahedron 1998, 54, 11255-11270. (h) Adrio, J.; Carretero, J. C. Tetrahedron 1998, 54, 1601-1614. (i) Enders, D.; Müller, S. F.; Raabe, G. Angew. Chem., Int. Ed. Engl. 1999, 38, 195-197. (j) Carretero, J. C.; Gómez Arrayás, R. Synlett 1999, 49-50.
50. Vinyl sulfones are versatile synthetic intermediates. For selected reviews, see: (a) Simpkins, N. S. Sulphones in Organic Synthesis; Pergamon Press: Oxford, 1993. (b) Fuchs, P. L.; Braish, T. F. Chem. Rev. 1986, 86, 903-917. For leading references, see: (c) Jackson, R. F. W.; Standen S. P.; Clegg, W. J. Chem. Soc., Perkin Trans. 1 1995, 149-156. (d) Garrido, J. L.; Alonso, I.; Carretero, J. C. J. Org. Chem. 1998, 63, 9406-9413. (e) Carretero, J. C.; Gómez Arrayás, R. J. Org. Chem. 1998, 63, 2993-3005. (f) Back, T. G.; Nakajima, K. J. Org. Chem. 1998, 63, 6566-6571. (g) Caturla, F.; Nájera, C. Tetrahedron 1998, 54, 11255-11270. (h) Adrio, J.; Carretero, J. C. Tetrahedron 1998, 54, 1601-1614. (i) Enders, D.; Müller, S. F.; Raabe, G. Angew. Chem., Int. Ed. Engl. 1999, 38, 195-197. (j) Carretero, J. C.; Gómez Arrayás, R. Synlett 1999, 49-50.
51. Vinyl sulfones are versatile synthetic intermediates. For selected reviews, see: (a) Simpkins, N. S. Sulphones in Organic Synthesis; Pergamon Press: Oxford, 1993. (b) Fuchs, P. L.; Braish, T. F. Chem. Rev. 1986, 86, 903-917. For leading references, see: (c) Jackson, R. F. W.; Standen S. P.; Clegg, W. J. Chem. Soc., Perkin Trans. 1 1995, 149-156. (d) Garrido, J. L.; Alonso, I.; Carretero, J. C. J. Org. Chem. 1998, 63, 9406-9413. (e) Carretero, J. C.; Gómez Arrayás, R. J. Org. Chem. 1998, 63, 2993-3005. (f) Back, T. G.; Nakajima, K. J. Org. Chem. 1998, 63, 6566-6571. (g) Caturla, F.; Nájera, C. Tetrahedron 1998, 54, 11255-11270. (h) Adrio, J.; Carretero, J. C. Tetrahedron 1998, 54, 1601-1614. (i) Enders, D.; Müller, S. F.; Raabe, G. Angew. Chem., Int. Ed. Engl. 1999, 38, 195-197. (j) Carretero, J. C.; Gómez Arrayás, R. Synlett 1999, 49-50.
52. Vinyl sulfones are versatile synthetic intermediates. For selected reviews, see: (a) Simpkins, N. S. Sulphones in Organic Synthesis; Pergamon Press: Oxford, 1993. (b) Fuchs, P. L.; Braish, T. F. Chem. Rev. 1986, 86, 903-917. For leading references, see: (c) Jackson, R. F. W.; Standen S. P.; Clegg, W. J. Chem. Soc., Perkin Trans. 1 1995, 149-156. (d) Garrido, J. L.; Alonso, I.; Carretero, J. C. J. Org. Chem. 1998, 63, 9406-9413. (e) Carretero, J. C.; Gómez Arrayás, R. J. Org. Chem. 1998, 63, 2993-3005. (f) Back, T. G.; Nakajima, K. J. Org. Chem. 1998, 63, 6566-6571. (g) Caturla, F.; Nájera, C. Tetrahedron 1998, 54, 11255-11270. (h) Adrio, J.; Carretero, J. C. Tetrahedron 1998, 54, 1601-1614. (i) Enders, D.; Müller, S. F.; Raabe, G. Angew. Chem., Int. Ed. Engl. 1999, 38, 195-197. (j) Carretero, J. C.; Gómez Arrayás, R. Synlett 1999, 49-50.
53. Vinyl sulfones are versatile synthetic intermediates. For selected reviews, see: (a) Simpkins, N. S. Sulphones in Organic Synthesis; Pergamon Press: Oxford, 1993. (b) Fuchs, P. L.; Braish, T. F. Chem. Rev. 1986, 86, 903-917. For leading references, see: (c) Jackson, R. F. W.; Standen S. P.; Clegg, W. J. Chem. Soc., Perkin Trans. 1 1995, 149-156. (d) Garrido, J. L.; Alonso, I.; Carretero, J. C. J. Org. Chem. 1998, 63, 9406-9413. (e) Carretero, J. C.; Gómez Arrayás, R. J. Org. Chem. 1998, 63, 2993-3005. (f) Back, T. G.; Nakajima, K. J. Org. Chem. 1998, 63, 6566-6571. (g) Caturla, F.; Nájera, C. Tetrahedron 1998, 54, 11255-11270. (h) Adrio, J.; Carretero, J. C. Tetrahedron 1998, 54, 1601-1614. (i) Enders, D.; Müller, S. F.; Raabe, G. Angew. Chem., Int. Ed. Engl. 1999, 38, 195-197. (j) Carretero, J. C.; Gómez Arrayás, R. Synlett 1999, 49-50.
54. Vinyl sulfones are versatile synthetic intermediates. For selected reviews, see: (a) Simpkins, N. S. Sulphones in Organic Synthesis; Pergamon Press: Oxford, 1993. (b) Fuchs, P. L.; Braish, T. F. Chem. Rev. 1986, 86, 903-917. For leading references, see: (c) Jackson, R. F. W.; Standen S. P.; Clegg, W. J. Chem. Soc., Perkin Trans. 1 1995, 149-156. (d) Garrido, J. L.; Alonso, I.; Carretero, J. C. J. Org. Chem. 1998, 63, 9406-9413. (e) Carretero, J. C.; Gómez Arrayás, R. J. Org. Chem. 1998, 63, 2993-3005. (f) Back, T. G.; Nakajima, K. J. Org. Chem. 1998, 63, 6566-6571. (g) Caturla, F.; Nájera, C. Tetrahedron 1998, 54, 11255-11270. (h) Adrio, J.; Carretero, J. C. Tetrahedron 1998, 54, 1601-1614. (i) Enders, D.; Müller, S. F.; Raabe, G. Angew. Chem., Int. Ed. Engl. 1999, 38, 195-197. (j) Carretero, J. C.; Gómez Arrayás, R. Synlett 1999, 49-50.
55. Vinyl sulfones are versatile synthetic intermediates. For selected reviews, see: (a) Simpkins, N. S. Sulphones in Organic Synthesis; Pergamon Press: Oxford, 1993. (b) Fuchs, P. L.; Braish, T. F. Chem. Rev. 1986, 86, 903-917. For leading references, see: (c) Jackson, R. F. W.; Standen S. P.; Clegg, W. J. Chem. Soc., Perkin Trans. 1 1995, 149-156. (d) Garrido, J. L.; Alonso, I.; Carretero, J. C. J. Org. Chem. 1998, 63, 9406-9413. (e) Carretero, J. C.; Gómez Arrayás, R. J. Org. Chem. 1998, 63, 2993-3005. (f) Back, T. G.; Nakajima, K. J. Org. Chem. 1998, 63, 6566-6571. (g) Caturla, F.; Nájera, C. Tetrahedron 1998, 54, 11255-11270. (h) Adrio, J.; Carretero, J. C. Tetrahedron 1998, 54, 1601-1614. (i) Enders, D.; Müller, S. F.; Raabe, G. Angew. Chem., Int. Ed. Engl. 1999, 38, 195-197. (j) Carretero, J. C.; Gómez Arrayás, R. Synlett 1999, 49-50.
56. Vinyl sulfones are versatile synthetic intermediates. For selected reviews, see: (a) Simpkins, N. S. Sulphones in Organic Synthesis; Pergamon Press: Oxford, 1993. (b) Fuchs, P. L.; Braish, T. F. Chem. Rev. 1986, 86, 903-917. For leading references, see: (c) Jackson, R. F. W.; Standen S. P.; Clegg, W. J. Chem. Soc., Perkin Trans. 1 1995, 149-156. (d) Garrido, J. L.; Alonso, I.; Carretero, J. C. J. Org. Chem. 1998, 63, 9406-9413. (e) Carretero, J. C.; Gómez Arrayás, R. J. Org. Chem. 1998, 63, 2993-3005. (f) Back, T. G.; Nakajima, K. J. Org. Chem. 1998, 63, 6566-6571. (g) Caturla, F.; Nájera, C. Tetrahedron 1998, 54, 11255-11270. (h) Adrio, J.; Carretero, J. C. Tetrahedron 1998, 54, 1601-1614. (i) Enders, D.; Müller, S. F.; Raabe, G. Angew. Chem., Int. Ed. Engl. 1999, 38, 195-197. (j) Carretero, J. C.; Gómez Arrayás, R. Synlett 1999, 49-50.
57. For leading references on the preparation of vinyl oxiranes, see: (a) Frohn, M.; Dalkiewicz, M.; Tu, Y.; Wang, Z.-X.; Shi, Y. J. Org. Chem. 1998, 63, 2948-2953. (b) Hu, S.; Jayaraman, S.; Oehlshlager, A. C. J. Org. Chem. 1998, 63, 8843-8849. (c) Ma, S.; Zhao, S. J. Am. Chem. Soc. 1999, 121, 7943-7944. (d) Ramachandran, P. V.; Krzeminski, M. P. Tetrahedron Lett. 1999, 40, 7879-7881. For leading references on synthetic applications of vinyl oxiranes, see: (e) Jung, M. E.; Marquez, R. Tetrahedron Lett. 1999, 40, 3129-3132. (f) Trost, B. M.; McEachern, E. J. J. Am. Chem. Soc. 1999, 121, 8649-8650. (g) Murphy, S. T.; Bencsik, J. R.; Johnson, C. R. Org. Lett. 1999, 1, 1483-1485. (h) Sasaki, M.; Inoue, M.; Takamatsu, K.; Tachibana, K. J. Org. Chem. 1999, 64, 9399-9415.
58. For leading references on the preparation of vinyl oxiranes, see: (a) Frohn, M.; Dalkiewicz, M.; Tu, Y.; Wang, Z.-X.; Shi, Y. J. Org. Chem. 1998, 63, 2948-2953. (b) Hu, S.; Jayaraman, S.; Oehlshlager, A. C. J. Org. Chem. 1998, 63, 8843-8849. (c) Ma, S.; Zhao, S. J. Am. Chem. Soc. 1999, 121, 7943-7944. (d) Ramachandran, P. V.; Krzeminski, M. P. Tetrahedron Lett. 1999, 40, 7879-7881. For leading references on synthetic applications of vinyl oxiranes, see: (e) Jung, M. E.; Marquez, R. Tetrahedron Lett. 1999, 40, 3129-3132. (f) Trost, B. M.; McEachern, E. J. J. Am. Chem. Soc. 1999, 121, 8649-8650. (g) Murphy, S. T.; Bencsik, J. R.; Johnson, C. R. Org. Lett. 1999, 1, 1483-1485. (h) Sasaki, M.; Inoue, M.; Takamatsu, K.; Tachibana, K. J. Org. Chem. 1999, 64, 9399-9415.
59. For leading references on the preparation of vinyl oxiranes, see: (a) Frohn, M.; Dalkiewicz, M.; Tu, Y.; Wang, Z.-X.; Shi, Y. J. Org. Chem. 1998, 63, 2948-2953. (b) Hu, S.; Jayaraman, S.; Oehlshlager, A. C. J. Org. Chem. 1998, 63, 8843-8849. (c) Ma, S.; Zhao, S. J. Am. Chem. Soc. 1999, 121, 7943-7944. (d) Ramachandran, P. V.; Krzeminski, M. P. Tetrahedron Lett. 1999, 40, 7879-7881. For leading references on synthetic applications of vinyl oxiranes, see: (e) Jung, M. E.; Marquez, R. Tetrahedron Lett. 1999, 40, 3129-3132. (f) Trost, B. M.; McEachern, E. J. J. Am. Chem. Soc. 1999, 121, 8649-8650. (g) Murphy, S. T.; Bencsik, J. R.; Johnson, C. R. Org. Lett. 1999, 1, 1483-1485. (h) Sasaki, M.; Inoue, M.; Takamatsu, K.; Tachibana, K. J. Org. Chem. 1999, 64, 9399-9415.
60. For leading references on the preparation of vinyl oxiranes, see: (a) Frohn, M.; Dalkiewicz, M.; Tu, Y.; Wang, Z.-X.; Shi, Y. J. Org. Chem. 1998, 63, 2948-2953. (b) Hu, S.; Jayaraman, S.; Oehlshlager, A. C. J. Org. Chem. 1998, 63, 8843-8849. (c) Ma, S.; Zhao, S. J. Am. Chem. Soc. 1999, 121, 7943-7944. (d) Ramachandran, P. V.; Krzeminski, M. P. Tetrahedron Lett. 1999, 40, 7879-7881. For leading references on synthetic applications of vinyl oxiranes, see: (e) Jung, M. E.; Marquez, R. Tetrahedron Lett. 1999, 40, 3129-3132. (f) Trost, B. M.; McEachern, E. J. J. Am. Chem. Soc. 1999, 121, 8649-8650. (g) Murphy, S. T.; Bencsik, J. R.; Johnson, C. R. Org. Lett. 1999, 1, 1483-1485. (h) Sasaki, M.; Inoue, M.; Takamatsu, K.; Tachibana, K. J. Org. Chem. 1999, 64, 9399-9415.
61. For leading references on the preparation of vinyl oxiranes, see: (a) Frohn, M.; Dalkiewicz, M.; Tu, Y.; Wang, Z.-X.; Shi, Y. J. Org. Chem. 1998, 63, 2948-2953. (b) Hu, S.; Jayaraman, S.; Oehlshlager, A. C. J. Org. Chem. 1998, 63, 8843-8849. (c) Ma, S.; Zhao, S. J. Am. Chem. Soc. 1999, 121, 7943-7944. (d) Ramachandran, P. V.; Krzeminski, M. P. Tetrahedron Lett. 1999, 40, 7879-7881. For leading references on synthetic applications of vinyl oxiranes, see: (e) Jung, M. E.; Marquez, R. Tetrahedron Lett. 1999, 40, 3129-3132. (f) Trost, B. M.; McEachern, E. J. J. Am. Chem. Soc. 1999, 121, 8649-8650. (g) Murphy, S. T.; Bencsik, J. R.; Johnson, C. R. Org. Lett. 1999, 1, 1483-1485. (h) Sasaki, M.; Inoue, M.; Takamatsu, K.; Tachibana, K. J. Org. Chem. 1999, 64, 9399-9415.
62. For leading references on the preparation of vinyl oxiranes, see: (a) Frohn, M.; Dalkiewicz, M.; Tu, Y.; Wang, Z.-X.; Shi, Y. J. Org. Chem. 1998, 63, 2948-2953. (b) Hu, S.; Jayaraman, S.; Oehlshlager, A. C. J. Org. Chem. 1998, 63, 8843-8849. (c) Ma, S.; Zhao, S. J. Am. Chem. Soc. 1999, 121, 7943-7944. (d) Ramachandran, P. V.; Krzeminski, M. P. Tetrahedron Lett. 1999, 40, 7879-7881. For leading references on synthetic applications of vinyl oxiranes, see: (e) Jung, M. E.; Marquez, R. Tetrahedron Lett. 1999, 40, 3129-3132. (f) Trost, B. M.; McEachern, E. J. J. Am. Chem. Soc. 1999, 121, 8649-8650. (g) Murphy, S. T.; Bencsik, J. R.; Johnson, C. R. Org. Lett. 1999, 1, 1483-1485. (h) Sasaki, M.; Inoue, M.; Takamatsu, K.; Tachibana, K. J. Org. Chem. 1999, 64, 9399-9415.
63. For leading references on the preparation of vinyl oxiranes, see: (a) Frohn, M.; Dalkiewicz, M.; Tu, Y.; Wang, Z.-X.; Shi, Y. J. Org. Chem. 1998, 63, 2948-2953. (b) Hu, S.; Jayaraman, S.; Oehlshlager, A. C. J. Org. Chem. 1998, 63, 8843-8849. (c) Ma, S.; Zhao, S. J. Am. Chem. Soc. 1999, 121, 7943-7944. (d) Ramachandran, P. V.; Krzeminski, M. P. Tetrahedron Lett. 1999, 40, 7879-7881. For leading references on synthetic applications of vinyl oxiranes, see: (e) Jung, M. E.; Marquez, R. Tetrahedron Lett. 1999, 40, 3129-3132. (f) Trost, B. M.; McEachern, E. J. J. Am. Chem. Soc. 1999, 121, 8649-8650. (g) Murphy, S. T.; Bencsik, J. R.; Johnson, C. R. Org. Lett. 1999, 1, 1483-1485. (h) Sasaki, M.; Inoue, M.; Takamatsu, K.; Tachibana, K. J. Org. Chem. 1999, 64, 9399-9415.
64. For leading references on the preparation of vinyl oxiranes, see: (a) Frohn, M.; Dalkiewicz, M.; Tu, Y.; Wang, Z.-X.; Shi, Y. J. Org. Chem. 1998, 63, 2948-2953. (b) Hu, S.; Jayaraman, S.; Oehlshlager, A. C. J. Org. Chem. 1998, 63,
65. For the original reports on α-metalation of vinyl sulfoxides, see: (a) Posner, G. H.; Tang, P. W.; Mallamo, J. P. Tetrahedron Lett. 1978, 3995-3998. (b) Okamura, H.; Mitsuhira, Y.; Miura, M.; Takei, H. Chem. Lett. 1978, 517-520. For the condensation between α-metalated vinyl sulfoxides and aldehydes, sec: (c) Posner, G. H.; Mallamo, J. P.; Miura, K.; Hulce, M. Pure Appl. Chem. 1981, 53, 2307-2314. (d) Cheng, H.-C.; Yang, T.-H. Tetrahedron Lett. 1990, 31, 673-676. Complete selectivity was found in one isolated example. (e) Solladié, G.; Moine, G. J. Am. Chem. Soc. 1984, 106, 6097-6098. (f) Fawcett, J.; House, S.; Jenkins, P. R.; Lawrence, N. J.; Russell, D. R. J. Chem. Soc., Perkin Trans. 1 1993, 67-73. For the intramolecular alkylation of α-sulfinyl vinyl carbanions, see: (g) Maezaki, N.; Izumi, M.; Yuyama, S.; Iwata, C.; Tanaka, T. Chem. Commun. 1999, 1825-1826.
66. For the original reports on α-metalation of vinyl sulfoxides, see: (a) Posner, G. H.; Tang, P. W.; Mallamo, J. P. Tetrahedron Lett. 1978, 3995-3998. (b) Okamura, H.; Mitsuhira, Y.; Miura, M.; Takei, H. Chem. Lett. 1978, 517-520. For the condensation between α-metalated vinyl sulfoxides and aldehydes, sec: (c) Posner, G. H.; Mallamo, J. P.; Miura, K.; Hulce, M. Pure Appl. Chem. 1981, 53, 2307-2314. (d) Cheng, H.-C.; Yang, T.-H. Tetrahedron Lett. 1990, 31, 673-676. Complete selectivity was found in one isolated example. (e) Solladié, G.; Moine, G. J. Am. Chem. Soc. 1984, 106, 6097-6098. (f) Fawcett, J.; House, S.; Jenkins, P. R.; Lawrence, N. J.; Russell, D. R. J. Chem. Soc., Perkin Trans. 1 1993, 67-73. For the intramolecular alkylation of α-sulfinyl vinyl carbanions, see: (g) Maezaki, N.; Izumi, M.; Yuyama, S.; Iwata, C.; Tanaka, T. Chem. Commun. 1999, 1825-1826.
67. For the original reports on α-metalation of vinyl sulfoxides, see: (a) Posner, G. H.; Tang, P. W.; Mallamo, J. P. Tetrahedron Lett. 1978, 3995-3998. (b) Okamura, H.; Mitsuhira, Y.; Miura, M.; Takei, H. Chem. Lett. 1978, 517-520. For the condensation between α-metalated vinyl sulfoxides and aldehydes, sec: (c) Posner, G. H.; Mallamo, J. P.; Miura, K.; Hulce, M. Pure Appl. Chem. 1981, 53, 2307-2314. (d) Cheng, H.-C.; Yang, T.-H. Tetrahedron Lett. 1990, 31, 673-676. Complete selectivity was found in one isolated example. (e) Solladié, G.; Moine, G. J. Am. Chem. Soc. 1984, 106, 6097-6098. (f) Fawcett, J.; House, S.; Jenkins, P. R.; Lawrence, N. J.; Russell, D. R. J. Chem. Soc., Perkin Trans. 1 1993, 67-73. For the intramolecular alkylation of α-sulfinyl vinyl carbanions, see: (g) Maezaki, N.; Izumi, M.; Yuyama, S.; Iwata, C.; Tanaka, T. Chem. Commun. 1999, 1825-1826.
68. For the original reports on α-metalation of vinyl sulfoxides, see: (a) Posner, G. H.; Tang, P. W.; Mallamo, J. P. Tetrahedron Lett. 1978, 3995-3998. (b) Okamura, H.; Mitsuhira, Y.; Miura, M.; Takei, H. Chem. Lett. 1978, 517-520. For the condensation between α-metalated vinyl sulfoxides and aldehydes, sec: (c) Posner, G. H.; Mallamo, J. P.; Miura, K.; Hulce, M. Pure Appl. Chem. 1981, 53, 2307-2314. (d) Cheng, H.-C.; Yang, T.-H. Tetrahedron Lett. 1990, 31, 673-676. Complete selectivity was found in one isolated example. (e) Solladié, G.; Moine, G. J. Am. Chem. Soc. 1984, 106, 6097-6098. (f) Fawcett, J.; House, S.; Jenkins, P. R.; Lawrence, N. J.; Russell, D. R. J. Chem. Soc., Perkin Trans. 1 1993, 67-73. For the intramolecular alkylation of α-sulfinyl vinyl carbanions, see: (g) Maezaki, N.; Izumi, M.; Yuyama, S.; Iwata, C.; Tanaka, T. Chem. Commun. 1999, 1825-1826.
69. For the original reports on α-metalation of vinyl sulfoxides, see: (a) Posner, G. H.; Tang, P. W.; Mallamo, J. P. Tetrahedron Lett. 1978, 3995-3998. (b) Okamura, H.; Mitsuhira, Y.; Miura, M.; Takei, H. Chem. Lett. 1978, 517-520. For the condensation between α-metalated vinyl sulfoxides and aldehydes, sec: (c) Posner, G. H.; Mallamo, J. P.; Miura, K.; Hulce, M. Pure Appl. Chem. 1981, 53, 2307-2314. (d) Cheng, H.-C.; Yang, T.-H. Tetrahedron Lett. 1990, 31, 673-676. Complete selectivity was found in one isolated example. (e) Solladié, G.; Moine, G. J. Am. Chem. Soc. 1984, 106, 6097-6098. (f) Fawcett, J.; House, S.; Jenkins, P. R.; Lawrence, N. J.; Russell, D. R. J. Chem. Soc., Perkin Trans. 1 1993, 67-73. For the intramolecular alkylation of α-sulfinyl vinyl carbanions, see: (g) Maezaki, N.; Izumi, M.; Yuyama, S.; Iwata, C.; Tanaka, T. Chem. Commun. 1999, 1825-1826.
70. For the original reports on α-metalation of vinyl sulfoxides, see: (a) Posner, G. H.; Tang, P. W.; Mallamo, J. P. Tetrahedron Lett. 1978, 3995-3998. (b) Okamura, H.; Mitsuhira, Y.; Miura, M.; Takei, H. Chem. Lett. 1978, 517-520. For the condensation between α-metalated vinyl sulfoxides and aldehydes, sec: (c) Posner, G. H.; Mallamo, J. P.; Miura, K.; Hulce, M. Pure Appl. Chem. 1981, 53, 2307-2314. (d) Cheng, H.-C.; Yang, T.-H. Tetrahedron Lett. 1990, 31, 673-676. Complete selectivity was found in one isolated example. (e) Solladié, G.; Moine, G. J. Am. Chem. Soc. 1984, 106, 6097-6098. (f) Fawcett, J.; House, S.; Jenkins, P. R.; Lawrence, N. J.; Russell, D. R. J. Chem. Soc., Perkin Trans. 1 1993, 67-73. For the intramolecular alkylation of α-sulfinyl vinyl carbanions, see: (g) Maezaki, N.; Izumi, M.; Yuyama, S.; Iwata, C.; Tanaka, T. Chem. Commun. 1999, 1825-1826.
71. For the original reports on α-metalation of vinyl sulfoxides, see: (a) Posner, G. H.; Tang, P. W.; Mallamo, J. P. Tetrahedron Lett. 1978, 3995-3998. (b) Okamura, H.; Mitsuhira, Y.; Miura, M.; Takei, H. Chem. Lett. 1978, 517-520. For the condensation between α-metalated vinyl sulfoxides and aldehydes, sec: (c) Posner, G. H.; Mallamo, J. P.; Miura, K.; Hulce, M. Pure Appl. Chem. 1981, 53, 2307-2314. (d) Cheng, H.-C.; Yang, T.-H. Tetrahedron Lett. 1990, 31, 673-676. Complete selectivity was found in one isolated example. (e) Solladié, G.; Moine, G. J. Am. Chem. Soc. 1984, 106, 6097-6098. (f) Fawcett, J.; House, S.; Jenkins, P. R.; Lawrence, N. J.; Russell, D. R. J. Chem. Soc., Perkin Trans. 1 1993, 67-73. For the intramolecular alkylation of α-sulfinyl vinyl carbanions, see: (g) Maezaki, N.; Izumi, M.; Yuyama, S.; Iwata, C.; Tanaka, T. Chem. Commun. 1999, 1825-1826.
72. Marino, J. P.; de Dios, A.; Anna, L. J.; Fernández de la Pradilla, R. J. Org. Chem. 1996, 61, 109-117.
73. Prepared in two steps from the commercially available enantiomerically pure ethyl esters (lactate and mandelate): Massad, S. K.; Hawkins, L. D.; Baker, D. C. J. Org. Chem. 1983, 48, 5180-5182.
74. Enantiomerically pure α-alkoxy aldehydes are readily available by several routes such as glycol cleavage or asymmetric dihydroxylation of terminal alkenes followed by selective hydroxyl protection and Dess -Martin oxidation. For recent examples, see: (a) Zhong, Y.-L-; Shing, T. K. M. J. Org. Chem. 1997, 62, 2622-2624. (b) Li, S.; Pang, J.; Wilson, W. K.; Schroepfer, G. J., Jr. Tetrahedron: Asymmetry 1999, 10, 1687- 1707.
75. Enantiomerically pure α-alkoxy aldehydes are readily available by several routes such as glycol cleavage or asymmetric dihydroxylation of terminal alkenes followed by selective hydroxyl protection and Dess - Martin oxidation. For recent examples, see: (a) Zhong, Y.-L-; Shing, T. K. M. J. Org. Chem. 1997, 62, 2622-2624. (b) Li, S.; Pang, J.; Wilson, W. K.; Schroepfer, G. J., Jr. Tetrahedron: Asymmetry 1999, 10, 1687-1707.
76. Prepared in one step from commercially available enantiomerically pure (+)-menthyl (R)-p-toluensulfinate or (-)-menthyl (S)-p-toluensulfinate by the method of Craig: Craig, D.; Daniels, K.; MacKenzie, A. R. Tetrahedron 1993, 49, 11263-11304. Lithiation of Z vinyl sulfoxides yields E lithio derivatives; there are conflicting reports on the configurational stability at sulfur in this process, see: (a) Posner, G. H. In Asymmetric Reactions and Processes in Chemistry; Eliel, E. L., Otsuka, S., Eds.; ACS Symposium Series No. 185; American Chemical Society: Washington, DC, 1982; p 142. (b) See refs 9f and 9g.
77. Prepared in one step from commercially available enantiomerically pure (+)-menthyl (R)-p-toluensulfinate or (-)-menthyl (S)-p- toluensulfinate by the method of Craig: Craig, D.; Daniels, K.; MacKenzie, A. R. Tetrahedron 1993, 49, 11263-11304. Lithiation of Z vinyl sulfoxides yields E lithio derivatives; there are conflicting reports on the configurational stability at sulfur in this process, see: (a) Posner, G. H. In Asymmetric Reactions and Processes in Chemistry; Eliel, E. L., Otsuka, S., Eds.; ACS Symposium Series No. 185; American Chemical Society: Washington, DC, 1982; p 142. (b) See refs 9f and 9g.
78. Prepared in one step from commercially available enantiomerically pure (+)-menthyl (R)-p-toluensulfinate or (-)-menthyl (S)-p- toluensulfinate by the method of Craig: Craig, D.; Daniels, K.; MacKenzie, A. R. Tetrahedron 1993, 49, 11263-11304. Lithiation of Z vinyl sulfoxides yields E lithio derivatives; there are conflicting reports on the configurational stability at sulfur in this process, see: (a) Posner, G. H. In Asymmetric Reactions and Processes in Chemistry; Eliel, E. L., Otsuka, S., Eds.; ACS Symposium Series No. 185; American Chemical Society: Washington, DC, 1982; p 142. (b) See refs 9f and 9g.
79. (a) Jones, S. S.; Reese, C. B. J. Chem. Soc., Perkin Trans. 1 1979, 2762-2764.
80. (b) Ogilvie, K. K.; Entwistle, D. W. Carbohydr. Res. 1981, 89, 203-210.
81. Enantiopure α-halo aldehydes are relatively difficult to prepare and particularly prone to undergo racemization under standard laboratory conditions. For the asymmetric synthesis of nonracemic a-fluoro aldehydes, see: (a) Davis, F. A.; Kasu, P. V.; Sundarababu, G.; Qi, H. J. Org. Chem. 1997, 62, 7546-7547. For the synthesis of related enantiomerically pure α-chloro and α-bromo aldehydes see: (b) Martín, V. S.; Palazón, J. M. Tetrahedron Lett. 1992, 33, 2399-2402. For protocols to generate these intermediates in situ, see: (c) Bailey, P. L.; Briggs, A. D.; Jackson, R. F. W.; Pietruska, J. J. Chem. Soc., Perkin Trans. 1 1898, 3359-3363. (d) Wang, S.; Howe, G. P.; Mahal, R. S.; Procter, G. Tetrahedron Lett. 1992, 33, 3351
82. Enantiopure α-halo aldehydes are relatively difficult to prepare and particularly prone to undergo racemization under standard laboratory conditions. For the asymmetric synthesis of nonracemic a-fluoro aldehydes, see: (a) Davis, F. A.; Kasu, P. V.; Sundarababu, G.; Qi, H. J. Org. Chem. 1997, 62, 7546-7547. For the synthesis of related enantiomerically pure α-chloro and α-bromo aldehydes see: (b) Martín, V. S.; Palazón, J. M. Tetrahedron Lett. 1992, 33, 2399-2402. For protocols to generate these intermediates in situ, see: (c) Bailey, P. L.; Briggs, A. D.; Jackson, R. F. W.; Pietruska, J. J. Chem. Soc., Perkin Trans. 1 1898, 3359-3363. (d) Wang, S.; Howe, G. P.; Mahal, R. S.; Procter, G. Tetrahedron Lett. 1992, 33, 3351
83. Enantiopure α-halo aldehydes are relatively difficult to prepare and particularly prone to undergo racemization under standard laboratory conditions. For the asymmetric synthesis of nonracemic a-fluoro aldehydes, see: (a) Davis, F. A.; Kasu, P. V.; Sundarababu, G.; Qi, H. J. Org. Chem. 1997, 62, 7546-7547. For the synthesis of related enantiomerically pure α-chloro and α-bromo aldehydes see: (b) Martín, V. S.; Palazón, J. M. Tetrahedron Lett. 1992, 33, 2399-2402. For protocols to generate these intermediates in situ, see: (c) Bailey, P. L.; Briggs, A. D.; Jackson, R. F. W.; Pietruska, J. J. Chem. Soc., Perkin Trans. 1 1898, 3359-3363. (d) Wang, S.; Howe, G. P.; Mahal, R. S.; Procter, G. Tetrahedron Lett. 1992, 33, 3351
84. Enantiopure α-halo aldehydes are relatively difficult to prepare and particularly prone to undergo racemization under standard laboratory conditions. For the asymmetric synthesis of nonracemic a-fluoro aldehydes, see: (a) Davis, F. A.; Kasu, P. V.; Sundarababu, G.; Qi, H. J. Org. Chem. 1997, 62, 7546-7547. For the synthesis of related enantiomerically pure α-chloro and α-bromo aldehydes see: (b) Martín, V. S.; Palazón, J. M. Tetrahedron Lett. 1992, 33, 2399-2402. For protocols to generate these intermediates in situ, see: (c) Bailey, P. L.; Briggs, A. D.; Jackson, R. F. W.; Pietruska, J. J. Chem. Soc., Perkin Trans. 1 1898, 3359-3363. (d) Wang, S.; Howe, G. P.; Mahal, R. S.; Procter, G. Tetrahedron Lett. 1992, 33, 3351
85. Prepared in one step by the method of Stevens: Stevens, C. L.; Farkans, E.; Gillis, B. J. J. Am. Chem. Soc. 1954, 76, 2695-2698.
86. 2 (Corey, E. J.; Nicolau, K. C.; Shibasaki, M.; Machida, Y.; Shiner, C. S. Tetrahedron Lett. 1975, 37, 3183-3186) led to a complex mixture of products.
87. The desired oxiranes 7e and 9b were obtained in fair yield by simply allowing the crude condensation mixture to warm to room temperature; however, separation of these diastereomers by chromatography was exceedingly difficult and therefore we settled for the use of pure chlorohydrins lia and 12a. Our initial experiments entailed addition of solid NaO-t-Bu to a cold (0°C) solution of 12a in THF. These conditions, particularly upon scale-up, gave very erratic results with low yields of oxirane 9b and complex reaction mixtures containing up to 50% of 1-p-tolylsulfinyl-2-hexene, presumably produced by fragmentation of 12a. The use of solid KO-t-Bu gave even more complex reaction mixtures. Fortunately, we found that the use of a preformed suspension of NaO-t-Bu in THF gave reproducible results.
88. N2′ addition of chlorohydrin 11a to vinyl epoxide 7e. The configuration at C-8 has not been determined.
89. These are standard values for vicinal coupling constants in oxiranes. See ref 6h for data of a variety of sulfinyl oxiranes.
90. 3SnH, AIBN, toluene, 100°C, 4 h), hoping to obtain sulfinyl alcohols closely related to those described in ref 5. Surprisingly, good yields of the corresponding enantiomeric sulfonyl chlorohydrins were obtained.
91. 3SnH, AIBN, toluene, 100°C, 4 h), hoping to obtain sulfinyl alcohols closely related to those described in ref 5. Surprisingly, good yields of the corresponding enantiomeric sulfonyl chlorohydrins were obtained.
92. Mengel, A.; Reiser, O. Chem. Rev. 1999, 99, 1191-1223. Moderate diastereoselectivities have been obtained (dr = 77:23-88: 12) in favor of anti chlorohydrins (Cram addition mode) in the condensation between standard nucleophiles and α-chloro aldehydes, see: (c) Frenking, G.; Köhler, K. F.; Reetz, M. T. Tetrahedron 1991, 43, 9005-9018.
93. Mengel, A.; Reiser, O. Chem. Rev. 1999, 99, 1191-1223. Moderate diastereoselectivities have been obtained (dr = 77:23-88: 12) in favor of anti chlorohydrins (Cram addition mode) in the condensation between standard nucleophiles and α-chloro aldehydes, see: (c) Frenking, G.; Köhler, K. F.; Reetz, M. T. Tetrahedron 1991, 43, 9005-9018.
94. For a discussion of a related allene formation, see: (a) Fernández de la Pradilla, R.; Rubio, M. B.; Marino, J. P.; Viso, A. Tetrahedron Lett. 1992, 33, 4985-4988. See also: (b) Delouvrié, B.; Lacôte, E.; Fensterbank, L.; Malacria, M. Tetrahedron Lett. 1999, 40, 3565-3568. (c) Satoh, T.; Kuramochi, Y.; Inoue, Y. Tetrahedron Lett. 1999, 40, 8815-8818.
95. For a discussion of a related allene formation, see: (a) Fernández de la Pradilla, R.; Rubio, M. B.; Marino, J. P.; Viso, A. Tetrahedron Lett. 1992, 33, 4985-4988. See also: (b) Delouvrié, B.; Lacôte, E.; Fensterbank, L.; Malacria, M. Tetrahedron Lett. 1999, 40, 3565-3568. (c) Satoh, T.; Kuramochi, Y.; Inoue, Y. Tetrahedron Lett. 1999, 40, 8815-8818.
96. For a discussion of a related allene formation, see: (a) Fernández de la Pradilla, R.; Rubio, M. B.; Marino, J. P.; Viso, A. Tetrahedron Lett. 1992, 33, 4985-4988. See also: (b) Delouvrié, B.; Lacôte, E.; Fensterbank, L.; Malacria, M. Tetrahedron Lett. 1999, 40, 3565-3568. (c) Satoh, T.; Kuramochi, Y.; Inoue, Y. Tetrahedron Lett. 1999, 40, 8815-8818.
97. (a) Initial attempts in THF resulted in recovery of starting material. (b) Cyanocuprates have been the subject of a long standing controversy regarding structure and reactivity aspects. For a recent discussion, see: Krause, N. Angew. Chem., Int. Ed. Engl. 1999, 38, 79-80.
98. 2-hybridized ligands often show a decreased regioselectivity in these processes. See: Marino, J. P.; Fernández de la Pradilla, R.; Laborde, E. J. Org. Chem. 1987, 52, 4898-4913.
99. N2′ adducts.
100. N2 products and allene byproduct obtained in this experiment may be due to the fact that commercial EtMgBr was used.
101. N2′ adduct is opposite to the stereochemical course.
102. (a) Martin, S. F.; Dodge, J. A. Tetrahedron Lett. 1991, 32, 3017-3020.
103. For reviews, see: (a) Hughes, D. L. Org. React. 1992, 42, 335-669. (b) Hughes, D. L. Org. Prep. Proc. Int. 1996, 28, 127-164. The choice of solvent proved to be critical; polar solvents such as DME or DMF afforded unreacted starting material and in benzene a 20% ratio of the desired product was obtained along with an 80% ratio of a product (2:1 mixture of isomers) of undetermined structure.
104. For reviews, see: (a) Hughes, D. L. Org. React. 1992, 42, 335- 669. (b) Hughes, D. L. Org. Prep. Proc. Int. 1996, 28, 127-164. The choice of solvent proved to be critical; polar solvents such as DME or DMF afforded unreacted starting material and in benzene a 20% ratio of the desired product was obtained along with an 80% ratio of a product (2:1 mixture of isomers) of undetermined structure.
105. 1H NMR (200 MHz) δ 0.62-1.75 (m, 21 H), 2.30 (m, 1 H), 2.43 (s, 3 H), 2.85 (m, 2 H), 6.26 (s, 1 H), 7.34 (d, 2 H, J = 8.4 Hz), 7.83 (d, 2 H, J = 8.4 Hz). (formula presented)
106. 1H NMR (200 MHz) δ 0.62-1.75 (m, 21 H), 2.30 (m, 1 H), 2.43 (s, 3 H), 2.85 (m, 2 H), 6.26 (s, 1 H), 7.34 (d, 2 H, J = 8.4 Hz), 7.83 (d, 2 H, J = 8.4 Hz). (formula presented)
107. N2′ processes on acyclic vinyl sulfones, see: (a) Auvray, P.; Knochel, P.; Normant, J. F. Tetrahedron 1988, 44, 6095-6106. (b) See also ref 5a.
108. N2′ processes on acyclic vinyl sulfones, see: (a) Auvray, P.; Knochel, P.; Normant, J. F. Tetrahedron 1988, 44, 6095-6106. (b) See also ref 5a.
109. N2′ displacements on cyclic vinyl sulfones, see: (a) Saddler, J. C.; Fuchs, P. L. J. Am. Chem. Soc. 1981, 103, 2112-2114. (b) Pan, Y.; Hardinger, S. A.; Fuchs, P. L. Synth. Commun. 1989, 19, 403-416. (c) Pan, Y.; Hutchinson, D. K.; Nautz, M. H.; Fuchs, P. L. Tetrahedron 1989, 45, 467-478. (d) Bäckvall, J. E.; Juntunen, S. K. J. Org. Chem. 1988, 53, 2398-2400. (e) Braish, T.; Saddler, J. C.; Fuchs P. L. J. Org. Chem. 1988, 53, 3647-3658. (f) Hardinger, S. A.; Fuchs, P. L. J. Org. Chem. 1987, 52, 2739-2749. (g) Arjona O.; de Dios, A.; Fernández de la Pradilla, R.; Plumet, J.; Viso, A. J. Org. Chem. 1994, 59, 3906-3916. (h) See ref 4i.
110. N2′ displacements on cyclic vinyl sulfones, see: (a) Saddler, J. C.; Fuchs, P. L. J. Am. Chem. Soc. 1981, 103, 2112- 2114. (b) Pan, Y.; Hardinger, S. A.; Fuchs, P. L. Synth. Commun. 1989, 19, 403-416. (c) Pan, Y.; Hutchinson, D. K.; Nautz, M. H.; Fuchs, P. L. Tetrahedron 1989, 45, 467-478. (d) Bäckvall, J. E.; Juntunen, S. K. J. Org. Chem. 1988, 53, 2398-2400. (e) Braish, T.; Saddler, J. C.; Fuchs P. L. J. Org. Chem. 1988, 53, 3647-3658. (f) Hardinger, S. A.; Fuchs, P. L. J. Org. Chem. 1987, 52, 2739-2749. (g) Arjona O.; de Dios, A.; Fernández de la Pradilla, R.; Plumet, J.; Viso, A. J. Org. Chem. 1994, 59, 3906-3916. (h) See ref 4i.
111. N2′ displacements on cyclic vinyl sulfones, see: (a) Saddler, J. C.; Fuchs, P. L. J. Am. Chem. Soc. 1981, 103, 2112- 2114. (b) Pan, Y.; Hardinger, S. A.; Fuchs, P. L. Synth. Commun. 1989, 19, 403-416. (c) Pan, Y.; Hutchinson, D. K.; Nautz, M. H.; Fuchs, P. L. Tetrahedron 1989, 45, 467-478. (d) Bäckvall, J. E.; Juntunen, S. K. J. Org. Chem. 1988, 53, 2398-2400. (e) Braish, T.; Saddler, J. C.; Fuchs P. L. J. Org. Chem. 1988, 53, 3647-3658. (f) Hardinger, S. A.; Fuchs, P. L. J. Org. Chem. 1987, 52, 2739-2749. (g) Arjona O.; de Dios, A.; Fernández de la Pradilla, R.; Plumet, J.; Viso, A. J. Org. Chem. 1994, 59, 3906-3916. (h) See ref 4i.
112. N2′ displacements on cyclic vinyl sulfones, see: (a) Saddler, J. C.; Fuchs, P. L. J. Am. Chem. Soc. 1981, 103, 2112- 2114. (b) Pan, Y.; Hardinger, S. A.; Fuchs, P. L. Synth. Commun. 1989, 19, 403-416. (c) Pan, Y.; Hutchinson, D. K.; Nautz, M. H.; Fuchs, P. L. Tetrahedron 1989, 45, 467-478. (d) Bäckvall, J. E.; Juntunen, S. K. J. Org. Chem. 1988, 53, 2398-2400. (e) Braish, T.; Saddler, J. C.; Fuchs P. L. J. Org. Chem. 1988, 53, 3647-3658. (f) Hardinger, S. A.; Fuchs, P. L. J. Org. Chem. 1987, 52, 2739-2749. (g) Arjona O.; de Dios, A.; Fernández de la Pradilla, R.; Plumet, J.; Viso, A. J. Org. Chem. 1994, 59, 3906-3916. (h) See ref 4i.
113. N2′ displacements on cyclic vinyl sulfones, see: (a) Saddler, J. C.; Fuchs, P. L. J. Am. Chem. Soc. 1981, 103, 2112- 2114. (b) Pan, Y.; Hardinger, S. A.; Fuchs, P. L. Synth. Commun. 1989, 19, 403-416. (c) Pan, Y.; Hutchinson, D. K.; Nautz, M. H.; Fuchs, P. L. Tetrahedron 1989, 45, 467-478. (d) Bäckvall, J. E.; Juntunen, S. K. J. Org. Chem. 1988, 53, 2398-2400. (e) Braish, T.; Saddler, J. C.; Fuchs P. L. J. Org. Chem. 1988, 53, 3647-3658. (f) Hardinger, S. A.; Fuchs, P. L. J. Org. Chem. 1987, 52, 2739-2749. (g) Arjona O.; de Dios, A.; Fernández de la Pradilla, R.; Plumet, J.; Viso, A. J. Org. Chem. 1994, 59, 3906-3916. (h) See ref 4i.
114. N2′ displacements on cyclic vinyl sulfones, see: (a) Saddler, J. C.; Fuchs, P. L. J. Am. Chem. Soc. 1981, 103, 2112- 2114. (b) Pan, Y.; Hardinger, S. A.; Fuchs, P. L. Synth. Commun. 1989, 19, 403-416. (c) Pan, Y.; Hutchinson, D. K.; Nautz, M. H.; Fuchs, P. L. Tetrahedron 1989, 45, 467-478. (d) Bäckvall, J. E.; Juntunen, S. K. J. Org. Chem. 1988, 53, 2398-2400. (e) Braish, T.; Saddler, J. C.; Fuchs P. L. J. Org. Chem. 1988, 53, 3647-3658. (f) Hardinger, S. A.; Fuchs, P. L. J. Org. Chem. 1987, 52, 2739-2749. (g) Arjona O.; de Dios, A.; Fernández de la Pradilla, R.; Plumet, J.; Viso, A. J. Org. Chem. 1994, 59, 3906-3916. (h) See ref 4i.
115. N2′ displacements on cyclic vinyl sulfones, see: (a) Saddler, J. C.; Fuchs, P. L. J. Am. Chem. Soc. 1981, 103, 2112- 2114. (b) Pan, Y.; Hardinger, S. A.; Fuchs, P. L. Synth. Commun. 1989, 19, 403-416. (c) Pan, Y.; Hutchinson, D. K.; Nautz, M. H.; Fuchs, P. L. Tetrahedron 1989, 45, 467-478. (d) Bäckvall, J. E.; Juntunen, S. K. J. Org. Chem. 1988, 53, 2398-2400. (e) Braish, T.; Saddler, J. C.; Fuchs P. L. J. Org. Chem. 1988, 53, 3647-3658. (f) Hardinger, S. A.; Fuchs, P. L. J. Org. Chem. 1987, 52, 2739-2749. (g) Arjona O.; de Dios, A.; Fernández de la Pradilla, R.; Plumet, J.; Viso, A. J. Org. Chem. 1994, 59, 3906-3916. (h) See ref 4i.
116. N2′ displacements on cyclic vinyl sulfones, see: (a) Saddler, J. C.; Fuchs, P. L. J. Am. Chem. Soc. 1981, 103, 2112- 2114. (b) Pan, Y.; Hardinger, S. A.; Fuchs, P. L. Synth. Commun. 1989, 19, 403-416. (c) Pan, Y.; Hutchinson, D. K.; Nautz, M. H.; Fuchs, P. L. Tetrahedron 1989, 45, 467-478. (d) Bäckvall, J. E.; Juntunen, S. K. J. Org. Chem. 1988, 53, 2398-2400. (e) Braish, T.; Saddler, J. C.; Fuchs P. L. J. Org. Chem. 1988, 53, 3647-3658. (f) Hardinger, S. A.; Fuchs, P. L. J. Org. Chem. 1987, 52, 2739-2749. (g) Arjona O.; de Dios, A.; Fernández de la Pradilla, R.; Plumet, J.; Viso, A. J. Org. Chem. 1994, 59, 3906-3916. (h) See ref 4i.
117. Iodo vinyl sulfide 24 was prepared from (phenylthio)acetylene (Magriotis, P. A.; Brown J. T. Org. Synth. 1998, 72, 252-264) using the procedure described: (a) Alexakis, A.; Cahiez, G.; Normant, J. F.; Villieras, J. Bull. Soc. Chim. Fr. 1977, 693-698. (b) Vermeer, P.; de Graaf, C.; Meijer, J. Recl. Trav. Chim. Pays-Bas 1974, 93, 24-25.
118. Iodo vinyl sulfide 24 was prepared from (phenylthio)acetylene (Magriotis, P. A.; Brown J. T. Org. Synth. 1998, 72, 252-264) using the procedure described: (a) Alexakis, A.; Cahiez, G.; Normant, J. F.; Villieras, J. Bull. Soc. Chim. Fr. 1977, 693-698. (b) Vermeer, P.; de Graaf, C.; Meijer, J. Recl. Trav. Chim. Pays-Bas 1974, 93, 24-25.
119. Iodo vinyl sulfide 24 was prepared from (phenylthio)acetylene (Magriotis, P. A.; Brown J. T. Org. Synth. 1998, 72, 252-264) using the procedure described: (a) Alexakis, A.; Cahiez, G.; Normant, J. F.; Villieras, J. Bull. Soc. Chim. Fr. 1977, 693-698. (b) Vermeer, P.; de Graaf, C.; Meijer, J. Recl. Trav. Chim. Pays-Bas 1974, 93, 24-25.
120. The unusual amount of silicon migration product 26 obtained in this experiment is likely due to the fact that the reaction mixture was allowed to warm to -20°C prior to quenching; this procedure was not optimized.
121. Although a definitive conclusion cannot be reached due to the difference in the aryl sulfide substituent (p-tolyl vs phenyl) the allylic proton of the deoxygenation product ent-28d′ had identical chemical shift to the allylic proton of the major isomer of the cuprate addition 28d.
122. Hoffman, R. W Chem. Rev. 1989, 89, 1841-1860.
123. For a computational treatment of the conformations of α,β-unsaturated sulfoxides, see: Tiezte, L. F.; Schuffenhauer, A.; Schreiner, P. R. J. Am. Chem. Soc. 1998, 120, 7952-7958, and references therein.
124. For mechanistic proposals, see: (a) Corey, E. J.; Boaz, N. W. Tetrahedron Lett. 1984, 25, 3063-3066. (b) Goering, H. L.; Kantner, S. S. J. Org. Chem. 1984, 49, 422-426.
125. For mechanistic proposals, see: (a) Corey, E. J.; Boaz, N. W. Tetrahedron Lett. 1984, 25, 3063-3066. (b) Goering, H. L.; Kantner, S. S. J. Org. Chem. 1984, 49, 422-426.
126. Evans, D. A.; Dart, M. J.; Duffy, J. L.; Yang, M. G. J. Am. Chem. Soc. 1990, 118, 4322-4343.
127. N2′ displacement on a cyclic epoxy vinyl sulfone with MeLi, see refs 32a and 32e.
128. N2′ displacement on a cyclic epoxy vinyl sulfone with MeLi, see refs 32a and 32e.
129. N2′ displacement on a cyclic epoxy vinyl sulfone with MeLi, see refs 32a and 32e.
130. N2′ displacement on a cyclic epoxy vinyl sulfone with MeLi, see refs 32a and 32e.
131. N2′ displacement on a cyclic epoxy vinyl sulfone with MeLi, see refs 32a and 32e.
132. For leading references on sulfonyl participation in chelated intermediates, see: (a) Yakura, T.; Tanaka, K.; Iwamoto, M.; Nameki, M.; Ikeda, M. Synlett 1999, 1313-1315. (b) Marcantoni, E.; Cingolani, S.; Bartoli, G.; Bosco, M.; Sambri, L J. Org. Chem. 1998, 63, 3624- 3630.
133. For leading references on sulfonyl participation in chelated intermediates, see: (a) Yakura, T.; Tanaka, K.; Iwamoto, M.; Nameki, M.; Ikeda, M. Synlett 1999, 1313-1315. (b) Marcantoni, E.; Cingolani, S.; Bartoli, G.; Bosco, M.; Sambri, L J. Org. Chem. 1998, 63, 3624-3630.
134. We thank one of the reviewers for pointing out the rationalizations shown in Scheme 10.