Synthesis of α-methyl kainic acid by stereospecific lithiation-dearomatizing cyclization of a chiral benzamide

Tetrahedron Letters

Volumn 44, Issue 16, 2003, Pages 3397-3400

  Clayden, Jonathan ^a   Knowles, Faye E ^a   Menet, Christel J ^a  

^a UNIVERSITY OF MANCHESTER   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ALPHA METHYLKAINIC ACID; BENZAMIDE; BENZYLLITHIUM; ISOINDOLE DERIVATIVE; KAINIC ACID DERIVATIVE; LITHIUM DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CHIRALITY; CYCLIZATION; LITHIATION; STEREOCHEMISTRY; STEREOSPECIFICITY; SYNTHESIS;

EID: 0037436992     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(03)00570-7     Document Type: Article

References (47)

1. In the sense of Zimmermann. See: Zimmerman H.E., Singer L., Thyagarajan B.S. J. Am. Chem. Soc. 81:1959;108.
2. March J. Advanced Organic Chemistry. 4th ed. 1992;Wiley, New York.
3. Gawley R.E. Tetrahedron Lett. 40:1999;4297.
4. Gawley R.E., Low E., Zhang Q., Harrris R. J. Am. Chem. Soc. 122:2000;3344.
5. For discussions, see: (a) Clayden, J. Organolithiums: Selectivity for Synthesis; Pergamon: Oxford, 2002; (b) Basu. A.; Thayumanavan, S. Angew. Chem., Int. Ed. 2002, 41, 716.
6. For discussions, see: (a) Clayden, J. Organolithiums: Selectivity for Synthesis; Pergamon: Oxford, 2002; (b) Basu. A.; Thayumanavan, S. Angew. Chem., Int. Ed. 2002, 41, 716.
7. Stereospecific deprotonation (with no external source of stereocontrol) yielding configurationally stable organolithiums is relatively rare [most examples generate tertiary N- or O-substituted organolithiums. See: (a) Faibish, N. C.; Park, Y. S.; Lee, S.; Beak, P. J. Am. Chem. Soc. 1997, 119, 11561; (b) Hara, O.; Ho, M.; Hamada, Y. Tetrahedron Lett. 1998, 39, 5537; (c) Krämer, T.; Hoppe, D. Tetrahedron Lett. 1987, 28, 5149; (d) Hoppe, D.; Carstens, A.; Krämer, T. Angew. Chem., Int. Ed. Engl. 1990, 29, 1424; (e) Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097; (f) Derwing, C.; Hoppe, D. Synthesis 1996, 149; (g) Hammerschmidt, F.; Hanninger, A. Chem. Ber. 1995, 128, 1069 but also (h) Hoppe, D.; Paetow, M.; Hintze, F. Angew. Chem., Int. Ed. Engl. 1993, 32, 394; (i) Kaiser, B.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 323] because, as Hoppe has pointed out (Hoppe, D.; Krämer, T. Angew. Chem., Int. Ed. Engl. 1986, 25, 160) factors promoting deprotonation are also conducive to configurational instability.
8. Stereospecific deprotonation (with no external source of stereocontrol) yielding configurationally stable organolithiums is relatively rare [most examples generate tertiary N- or O-substituted organolithiums. See: (a) Faibish, N. C.; Park, Y. S.; Lee, S.; Beak, P. J. Am. Chem. Soc. 1997, 119, 11561; (b) Hara, O.; Ho, M.; Hamada, Y. Tetrahedron Lett. 1998, 39, 5537; (c) Krämer, T.; Hoppe, D. Tetrahedron Lett. 1987, 28, 5149; (d) Hoppe, D.; Carstens, A.; Krämer, T. Angew. Chem., Int. Ed. Engl. 1990, 29, 1424; (e) Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097; (f) Derwing, C.; Hoppe, D. Synthesis 1996, 149; (g) Hammerschmidt, F.; Hanninger, A. Chem. Ber. 1995, 128, 1069 but also (h) Hoppe, D.; Paetow, M.; Hintze, F. Angew. Chem., Int. Ed. Engl. 1993, 32, 394; (i) Kaiser, B.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 323] because, as Hoppe has pointed out (Hoppe, D.; Krämer, T. Angew. Chem., Int. Ed. Engl. 1986, 25, 160) factors promoting deprotonation are also conducive to configurational instability.
9. Stereospecific deprotonation (with no external source of stereocontrol) yielding configurationally stable organolithiums is relatively rare [most examples generate tertiary N- or O-substituted organolithiums. See: (a) Faibish, N. C.; Park, Y. S.; Lee, S.; Beak, P. J. Am. Chem. Soc. 1997, 119, 11561; (b) Hara, O.; Ho, M.; Hamada, Y. Tetrahedron Lett. 1998, 39, 5537; (c) Krämer, T.; Hoppe, D. Tetrahedron Lett. 1987, 28, 5149; (d) Hoppe, D.; Carstens, A.; Krämer, T. Angew. Chem., Int. Ed. Engl. 1990, 29, 1424; (e) Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097; (f) Derwing, C.; Hoppe, D. Synthesis 1996, 149; (g) Hammerschmidt, F.; Hanninger, A. Chem. Ber. 1995, 128, 1069 but also (h) Hoppe, D.; Paetow, M.; Hintze, F. Angew. Chem., Int. Ed. Engl. 1993, 32, 394; (i) Kaiser, B.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 323] because, as Hoppe has pointed out (Hoppe, D.; Krämer, T. Angew. Chem., Int. Ed. Engl. 1986, 25, 160) factors promoting deprotonation are also conducive to configurational instability.
10. Stereospecific deprotonation (with no external source of stereocontrol) yielding configurationally stable organolithiums is relatively rare [most examples generate tertiary N- or O-substituted organolithiums. See: (a) Faibish, N. C.; Park, Y. S.; Lee, S.; Beak, P. J. Am. Chem. Soc. 1997, 119, 11561; (b) Hara, O.; Ho, M.; Hamada, Y. Tetrahedron Lett. 1998, 39, 5537; (c) Krämer, T.; Hoppe, D. Tetrahedron Lett. 1987, 28, 5149; (d) Hoppe, D.; Carstens, A.; Krämer, T. Angew. Chem., Int. Ed. Engl. 1990, 29, 1424; (e) Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097; (f) Derwing, C.; Hoppe, D. Synthesis 1996, 149; (g) Hammerschmidt, F.; Hanninger, A. Chem. Ber. 1995, 128, 1069 but also (h) Hoppe, D.; Paetow, M.; Hintze, F. Angew. Chem., Int. Ed. Engl. 1993, 32, 394; (i) Kaiser, B.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 323] because, as Hoppe has pointed out (Hoppe, D.; Krämer, T. Angew. Chem., Int. Ed. Engl. 1986, 25, 160) factors promoting deprotonation are also conducive to configurational instability.
11. Stereospecific deprotonation (with no external source of stereocontrol) yielding configurationally stable organolithiums is relatively rare [most examples generate tertiary N- or O-substituted organolithiums. See: (a) Faibish, N. C.; Park, Y. S.; Lee, S.; Beak, P. J. Am. Chem. Soc. 1997, 119, 11561; (b) Hara, O.; Ho, M.; Hamada, Y. Tetrahedron Lett. 1998, 39, 5537; (c) Krämer, T.; Hoppe, D. Tetrahedron Lett. 1987, 28, 5149; (d) Hoppe, D.; Carstens, A.; Krämer, T. Angew. Chem., Int. Ed. Engl. 1990, 29, 1424; (e) Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097; (f) Derwing, C.; Hoppe, D. Synthesis 1996, 149; (g) Hammerschmidt, F.; Hanninger, A. Chem. Ber. 1995, 128, 1069 but also (h) Hoppe, D.; Paetow, M.; Hintze, F. Angew. Chem., Int. Ed. Engl. 1993, 32, 394; (i) Kaiser, B.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 323] because, as Hoppe has pointed out (Hoppe, D.; Krämer, T. Angew. Chem., Int. Ed. Engl. 1986, 25, 160) factors promoting deprotonation are also conducive to configurational instability.
12. Stereospecific deprotonation (with no external source of stereocontrol) yielding configurationally stable organolithiums is relatively rare [most examples generate tertiary N- or O-substituted organolithiums. See: (a) Faibish, N. C.; Park, Y. S.; Lee, S.; Beak, P. J. Am. Chem. Soc. 1997, 119, 11561; (b) Hara, O.; Ho, M.; Hamada, Y. Tetrahedron Lett. 1998, 39, 5537; (c) Krämer, T.; Hoppe, D. Tetrahedron Lett. 1987, 28, 5149; (d) Hoppe, D.; Carstens, A.; Krämer, T. Angew. Chem., Int. Ed. Engl. 1990, 29, 1424; (e) Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097; (f) Derwing, C.; Hoppe, D. Synthesis 1996, 149; (g) Hammerschmidt, F.; Hanninger, A. Chem. Ber. 1995, 128, 1069 but also (h) Hoppe, D.; Paetow, M.; Hintze, F. Angew. Chem., Int. Ed. Engl. 1993, 32, 394; (i) Kaiser, B.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 323] because, as Hoppe has pointed out (Hoppe, D.; Krämer, T. Angew. Chem., Int. Ed. Engl. 1986, 25, 160) factors promoting deprotonation are also conducive to configurational instability.
13. Stereospecific deprotonation (with no external source of stereocontrol) yielding configurationally stable organolithiums is relatively rare [most examples generate tertiary N- or O-substituted organolithiums. See: (a) Faibish, N. C.; Park, Y. S.; Lee, S.; Beak, P. J. Am. Chem. Soc. 1997, 119, 11561; (b) Hara, O.; Ho, M.; Hamada, Y. Tetrahedron Lett. 1998, 39, 5537; (c) Krämer, T.; Hoppe, D. Tetrahedron Lett. 1987, 28, 5149; (d) Hoppe, D.; Carstens, A.; Krämer, T. Angew. Chem., Int. Ed. Engl. 1990, 29, 1424; (e) Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097; (f) Derwing, C.; Hoppe, D. Synthesis 1996, 149; (g) Hammerschmidt, F.; Hanninger, A. Chem. Ber. 1995, 128, 1069 but also (h) Hoppe, D.; Paetow, M.; Hintze, F. Angew. Chem., Int. Ed. Engl. 1993, 32, 394; (i) Kaiser, B.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 323] because, as Hoppe has pointed out (Hoppe, D.; Krämer, T. Angew. Chem., Int. Ed. Engl. 1986, 25, 160) factors promoting deprotonation are also conducive to configurational instability.
14. Stereospecific deprotonation (with no external source of stereocontrol) yielding configurationally stable organolithiums is relatively rare [most examples generate tertiary N- or O-substituted organolithiums. See: (a) Faibish, N. C.; Park, Y. S.; Lee, S.; Beak, P. J. Am. Chem. Soc. 1997, 119, 11561; (b) Hara, O.; Ho, M.; Hamada, Y. Tetrahedron Lett. 1998, 39, 5537; (c) Krämer, T.; Hoppe, D. Tetrahedron Lett. 1987, 28, 5149; (d) Hoppe, D.; Carstens, A.; Krämer, T. Angew. Chem., Int. Ed. Engl. 1990, 29, 1424; (e) Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097; (f) Derwing, C.; Hoppe, D. Synthesis 1996, 149; (g) Hammerschmidt, F.; Hanninger, A. Chem. Ber. 1995, 128, 1069 but also (h) Hoppe, D.; Paetow, M.; Hintze, F. Angew. Chem., Int. Ed. Engl. 1993, 32, 394; (i) Kaiser, B.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 323] because, as Hoppe has pointed out (Hoppe, D.; Krämer, T. Angew. Chem., Int. Ed. Engl. 1986, 25, 160) factors promoting deprotonation are also conducive to configurational instability.
15. Stereospecific deprotonation (with no external source of stereocontrol) yielding configurationally stable organolithiums is relatively rare [most examples generate tertiary N- or O-substituted organolithiums. See: (a) Faibish, N. C.; Park, Y. S.; Lee, S.; Beak, P. J. Am. Chem. Soc. 1997, 119, 11561; (b) Hara, O.; Ho, M.; Hamada, Y. Tetrahedron Lett. 1998, 39, 5537; (c) Krämer, T.; Hoppe, D. Tetrahedron Lett. 1987, 28, 5149; (d) Hoppe, D.; Carstens, A.; Krämer, T. Angew. Chem., Int. Ed. Engl. 1990, 29, 1424; (e) Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097; (f) Derwing, C.; Hoppe, D. Synthesis 1996, 149; (g) Hammerschmidt, F.; Hanninger, A. Chem. Ber. 1995, 128, 1069 but also (h) Hoppe, D.; Paetow, M.; Hintze, F. Angew. Chem., Int. Ed. Engl. 1993, 32, 394; (i) Kaiser, B.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 323] because, as Hoppe has pointed out (Hoppe, D.; Krämer, T. Angew. Chem., Int. Ed. Engl. 1986, 25, 160) factors promoting deprotonation are also conducive to configurational instability.
16. Lithiated amides [(a) Ahmed, A.; Clayden, J.; Rowley, M. J. Chem. Soc., Chem. Commun. 1998, 297; (b) Ahmed, A.; Clayden, J.; Yasin, S. A. Chem. Commun. 1999, 231; (c) Clayden, J.; Menet, C. J.; Mansfield, D. J. Org. Lett. 2000, 2, 4229; (d) Clayden, J.; Tchabanenko, K.; Yasin, S. A.; Turnbull, M. D. Synlett 2001, 302; (e) Clayden, J.; Purewal, S.; Helliwell, M.; Mantell, S. J. Angew. Chem. Int. Ed. 2002, 41, 1091], sulfones [(f) Crandall, J. K.; Ayers, T. A. J. Org. Chem. 1992, 57, 2993], sulfonamides [(g) Aggarwal, V. K.; Ferrara, M. Org. Lett. 2000, 2, 4107; (h) Aggarwal, V. K.; Alonso, E.; Ferrara, M.; Spey, S. E. J. Org. Chem. 2002, 67, 2335; (i) Breternitz, H.-J.; Schaumann, E.; Adiwidjaja, G. Tetrahedron Lett. 1991, 32, 1299] and phosophonamides [(j) Fernández, I.; Ortiz, F. L.; Tejerina, B.; Granda, S. G. Org. Lett. 2001, 3, 1339; (k) Gómez, G. R.; Ortiz, F. L. Synlett 2002, 781] undergo anionic cyclizations with loss of aromaticity. For a review, see: Ref. 3a.
17. Lithiated amides [(a) Ahmed, A.; Clayden, J.; Rowley, M. J. Chem. Soc., Chem. Commun. 1998, 297; (b) Ahmed, A.; Clayden, J.; Yasin, S. A. Chem. Commun. 1999, 231; (c) Clayden, J.; Menet, C. J.; Mansfield, D. J. Org. Lett. 2000, 2, 4229; (d) Clayden, J.; Tchabanenko, K.; Yasin, S. A.; Turnbull, M. D. Synlett 2001, 302; (e) Clayden, J.; Purewal, S.; Helliwell, M.; Mantell, S. J. Angew. Chem. Int. Ed. 2002, 41, 1091], sulfones [(f) Crandall, J. K.; Ayers, T. A. J. Org. Chem. 1992, 57, 2993], sulfonamides [(g) Aggarwal, V. K.; Ferrara, M. Org. Lett. 2000, 2, 4107; (h) Aggarwal, V. K.; Alonso, E.; Ferrara, M.; Spey, S. E. J. Org. Chem. 2002, 67, 2335; (i) Breternitz, H.-J.; Schaumann, E.; Adiwidjaja, G. Tetrahedron Lett. 1991, 32, 1299] and phosophonamides [(j) Fernández, I.; Ortiz, F. L.; Tejerina, B.; Granda, S. G. Org. Lett. 2001, 3, 1339; (k) Gómez, G. R.; Ortiz, F. L. Synlett 2002, 781] undergo anionic cyclizations with loss of aromaticity. For a review, see: Ref. 3a.
18. Lithiated amides [(a) Ahmed, A.; Clayden, J.; Rowley, M. J. Chem. Soc., Chem. Commun. 1998, 297; (b) Ahmed, A.; Clayden, J.; Yasin, S. A. Chem. Commun. 1999, 231; (c) Clayden, J.; Menet, C. J.; Mansfield, D. J. Org. Lett. 2000, 2, 4229; (d) Clayden, J.; Tchabanenko, K.; Yasin, S. A.; Turnbull, M. D. Synlett 2001, 302; (e) Clayden, J.; Purewal, S.; Helliwell, M.; Mantell, S. J. Angew. Chem. Int. Ed. 2002, 41, 1091], sulfones [(f) Crandall, J. K.; Ayers, T. A. J. Org. Chem. 1992, 57, 2993], sulfonamides [(g) Aggarwal, V. K.; Ferrara, M. Org. Lett. 2000, 2, 4107; (h) Aggarwal, V. K.; Alonso, E.; Ferrara, M.; Spey, S. E. J. Org. Chem. 2002, 67, 2335; (i) Breternitz, H.-J.; Schaumann, E.; Adiwidjaja, G. Tetrahedron Lett. 1991, 32, 1299] and phosophonamides [(j) Fernández, I.; Ortiz, F. L.; Tejerina, B.; Granda, S. G. Org. Lett. 2001, 3, 1339; (k) Gómez, G. R.; Ortiz, F. L. Synlett 2002, 781] undergo anionic cyclizations with loss of aromaticity. For a review, see: Ref. 3a.
19. Lithiated amides [(a) Ahmed, A.; Clayden, J.; Rowley, M. J. Chem. Soc., Chem. Commun. 1998, 297; (b) Ahmed, A.; Clayden, J.; Yasin, S. A. Chem. Commun. 1999, 231; (c) Clayden, J.; Menet, C. J.; Mansfield, D. J. Org. Lett. 2000, 2, 4229; (d) Clayden, J.; Tchabanenko, K.; Yasin, S. A.; Turnbull, M. D. Synlett 2001, 302; (e) Clayden, J.; Purewal, S.; Helliwell, M.; Mantell, S. J. Angew. Chem. Int. Ed. 2002, 41, 1091], sulfones [(f) Crandall, J. K.; Ayers, T. A. J. Org. Chem. 1992, 57, 2993], sulfonamides [(g) Aggarwal, V. K.; Ferrara, M. Org. Lett. 2000, 2, 4107; (h) Aggarwal, V. K.; Alonso, E.; Ferrara, M.; Spey, S. E. J. Org. Chem. 2002, 67, 2335; (i) Breternitz, H.-J.; Schaumann, E.; Adiwidjaja, G. Tetrahedron Lett. 1991, 32, 1299] and phosophonamides [(j) Fernández, I.; Ortiz, F. L.; Tejerina, B.; Granda, S. G. Org. Lett. 2001, 3, 1339; (k) Gómez, G. R.; Ortiz, F. L. Synlett 2002, 781] undergo anionic cyclizations with loss of aromaticity. For a review, see: Ref. 3a.
20. Lithiated amides [(a) Ahmed, A.; Clayden, J.; Rowley, M. J. Chem. Soc., Chem. Commun. 1998, 297; (b) Ahmed, A.; Clayden, J.; Yasin, S. A. Chem. Commun. 1999, 231; (c) Clayden, J.; Menet, C. J.; Mansfield, D. J. Org. Lett. 2000, 2, 4229; (d) Clayden, J.; Tchabanenko, K.; Yasin, S. A.; Turnbull, M. D. Synlett 2001, 302; (e) Clayden, J.; Purewal, S.; Helliwell, M.; Mantell, S. J. Angew. Chem. Int. Ed. 2002, 41, 1091], sulfones [(f) Crandall, J. K.; Ayers, T. A. J. Org. Chem. 1992, 57, 2993], sulfonamides [(g) Aggarwal, V. K.; Ferrara, M. Org. Lett. 2000, 2, 4107; (h) Aggarwal, V. K.; Alonso, E.; Ferrara, M.; Spey, S. E. J. Org. Chem. 2002, 67, 2335; (i) Breternitz, H.-J.; Schaumann, E.; Adiwidjaja, G. Tetrahedron Lett. 1991, 32, 1299] and phosophonamides [(j) Fernández, I.; Ortiz, F. L.; Tejerina, B.; Granda, S. G. Org. Lett. 2001, 3, 1339; (k) Gómez, G. R.; Ortiz, F. L. Synlett 2002, 781] undergo anionic cyclizations with loss of aromaticity. For a review, see: Ref. 3a.
21. Lithiated amides [(a) Ahmed, A.; Clayden, J.; Rowley, M. J. Chem. Soc., Chem. Commun. 1998, 297; (b) Ahmed, A.; Clayden, J.; Yasin, S. A. Chem. Commun. 1999, 231; (c) Clayden, J.; Menet, C. J.; Mansfield, D. J. Org. Lett. 2000, 2, 4229; (d) Clayden, J.; Tchabanenko, K.; Yasin, S. A.; Turnbull, M. D. Synlett 2001, 302; (e) Clayden, J.; Purewal, S.; Helliwell, M.; Mantell, S. J. Angew. Chem. Int. Ed. 2002, 41, 1091], sulfones [(f) Crandall, J. K.; Ayers, T. A. J. Org. Chem. 1992, 57, 2993], sulfonamides [(g) Aggarwal, V. K.; Ferrara, M. Org. Lett. 2000, 2, 4107; (h) Aggarwal, V. K.; Alonso, E.; Ferrara, M.; Spey, S. E. J. Org. Chem. 2002, 67, 2335; (i) Breternitz, H.-J.; Schaumann, E.; Adiwidjaja, G. Tetrahedron Lett. 1991, 32, 1299] and phosophonamides [(j) Fernández, I.; Ortiz, F. L.; Tejerina, B.; Granda, S. G. Org. Lett. 2001, 3, 1339; (k) Gómez, G. R.; Ortiz, F. L. Synlett 2002, 781] undergo anionic cyclizations with loss of aromaticity. For a review, see: Ref. 3a.
22. Lithiated amides [(a) Ahmed, A.; Clayden, J.; Rowley, M. J. Chem. Soc., Chem. Commun. 1998, 297; (b) Ahmed, A.; Clayden, J.; Yasin, S. A. Chem. Commun. 1999, 231; (c) Clayden, J.; Menet, C. J.; Mansfield, D. J. Org. Lett. 2000, 2, 4229; (d) Clayden, J.; Tchabanenko, K.; Yasin, S. A.; Turnbull, M. D. Synlett 2001, 302; (e) Clayden, J.; Purewal, S.; Helliwell, M.; Mantell, S. J. Angew. Chem. Int. Ed. 2002, 41, 1091], sulfones [(f) Crandall, J. K.; Ayers, T. A. J. Org. Chem. 1992, 57, 2993], sulfonamides [(g) Aggarwal, V. K.; Ferrara, M. Org. Lett. 2000, 2, 4107; (h) Aggarwal, V. K.; Alonso, E.; Ferrara, M.; Spey, S. E. J. Org. Chem. 2002, 67, 2335; (i) Breternitz, H.-J.; Schaumann, E.; Adiwidjaja, G. Tetrahedron Lett. 1991, 32, 1299] and phosophonamides [(j) Fernández, I.; Ortiz, F. L.; Tejerina, B.; Granda, S. G. Org. Lett. 2001, 3, 1339; (k) Gómez, G. R.; Ortiz, F. L. Synlett 2002, 781] undergo anionic cyclizations with loss of aromaticity. For a review, see: Ref. 3a.
23. Lithiated amides [(a) Ahmed, A.; Clayden, J.; Rowley, M. J. Chem. Soc., Chem. Commun. 1998, 297; (b) Ahmed, A.; Clayden, J.; Yasin, S. A. Chem. Commun. 1999, 231; (c) Clayden, J.; Menet, C. J.; Mansfield, D. J. Org. Lett. 2000, 2, 4229; (d) Clayden, J.; Tchabanenko, K.; Yasin, S. A.; Turnbull, M. D. Synlett 2001, 302; (e) Clayden, J.; Purewal, S.; Helliwell, M.; Mantell, S. J. Angew. Chem. Int. Ed. 2002, 41, 1091], sulfones [(f) Crandall, J. K.; Ayers, T. A. J. Org. Chem. 1992, 57, 2993], sulfonamides [(g) Aggarwal, V. K.; Ferrara, M. Org. Lett. 2000, 2, 4107; (h) Aggarwal, V. K.; Alonso, E.; Ferrara, M.; Spey, S. E. J. Org. Chem. 2002, 67, 2335; (i) Breternitz, H.-J.; Schaumann, E.; Adiwidjaja, G. Tetrahedron Lett. 1991, 32, 1299] and phosophonamides [(j) Fernández, I.; Ortiz, F. L.; Tejerina, B.; Granda, S. G. Org. Lett. 2001, 3, 1339; (k) Gómez, G. R.; Ortiz, F. L. Synlett 2002, 781] undergo anionic cyclizations with loss of aromaticity. For a review, see: Ref. 3a.
24. Lithiated amides [(a) Ahmed, A.; Clayden, J.; Rowley, M. J. Chem. Soc., Chem. Commun. 1998, 297; (b) Ahmed, A.; Clayden, J.; Yasin, S. A. Chem. Commun. 1999, 231; (c) Clayden, J.; Menet, C. J.; Mansfield, D. J. Org. Lett. 2000, 2, 4229; (d) Clayden, J.; Tchabanenko, K.; Yasin, S. A.; Turnbull, M. D. Synlett 2001, 302; (e) Clayden, J.; Purewal, S.; Helliwell, M.; Mantell, S. J. Angew. Chem. Int. Ed. 2002, 41, 1091], sulfones [(f) Crandall, J. K.; Ayers, T. A. J. Org. Chem. 1992, 57, 2993], sulfonamides [(g) Aggarwal, V. K.; Ferrara, M. Org. Lett. 2000, 2, 4107; (h) Aggarwal, V. K.; Alonso, E.; Ferrara, M.; Spey, S. E. J. Org. Chem. 2002, 67, 2335; (i) Breternitz, H.-J.; Schaumann, E.; Adiwidjaja, G. Tetrahedron Lett. 1991, 32, 1299] and phosophonamides [(j) Fernández, I.; Ortiz, F. L.; Tejerina, B.; Granda, S. G. Org. Lett. 2001, 3, 1339; (k) Gómez, G. R.; Ortiz, F. L. Synlett 2002, 781] undergo anionic cyclizations with loss of aromaticity. For a review, see: Ref. 3a.
25. Lithiated amides [(a) Ahmed, A.; Clayden, J.; Rowley, M. J. Chem. Soc., Chem. Commun. 1998, 297; (b) Ahmed, A.; Clayden, J.; Yasin, S. A. Chem. Commun. 1999, 231; (c) Clayden, J.; Menet, C. J.; Mansfield, D. J. Org. Lett. 2000, 2, 4229; (d) Clayden, J.; Tchabanenko, K.; Yasin, S. A.; Turnbull, M. D. Synlett 2001, 302; (e) Clayden, J.; Purewal, S.; Helliwell, M.; Mantell, S. J. Angew. Chem. Int. Ed. 2002, 41, 1091], sulfones [(f) Crandall, J. K.; Ayers, T. A. J. Org. Chem. 1992, 57, 2993], sulfonamides [(g) Aggarwal, V. K.; Ferrara, M. Org. Lett. 2000, 2, 4107; (h) Aggarwal, V. K.; Alonso, E.; Ferrara, M.; Spey, S. E. J. Org. Chem. 2002, 67, 2335; (i) Breternitz, H.-J.; Schaumann, E.; Adiwidjaja, G. Tetrahedron Lett. 1991, 32, 1299] and phosophonamides [(j) Fernández, I.; Ortiz, F. L.; Tejerina, B.; Granda, S. G. Org. Lett. 2001, 3, 1339; (k) Gómez, G. R.; Ortiz, F. L. Synlett 2002, 781] undergo anionic cyclizations with loss of aromaticity. For a review, see: Ref. 3a.
26. Lithiated amides [(a) Ahmed, A.; Clayden, J.; Rowley, M. J. Chem. Soc., Chem. Commun. 1998, 297; (b) Ahmed, A.; Clayden, J.; Yasin, S. A. Chem. Commun. 1999, 231; (c) Clayden, J.; Menet, C. J.; Mansfield, D. J. Org. Lett. 2000, 2, 4229; (d) Clayden, J.; Tchabanenko, K.; Yasin, S. A.; Turnbull, M. D. Synlett 2001, 302; (e) Clayden, J.; Purewal, S.; Helliwell, M.; Mantell, S. J. Angew. Chem. Int. Ed. 2002, 41, 1091], sulfones [(f) Crandall, J. K.; Ayers, T. A. J. Org. Chem. 1992, 57, 2993], sulfonamides [(g) Aggarwal, V. K.; Ferrara, M. Org. Lett. 2000, 2, 4107; (h) Aggarwal, V. K.; Alonso, E.; Ferrara, M.; Spey, S. E. J. Org. Chem. 2002, 67, 2335; (i) Breternitz, H.-J.; Schaumann, E.; Adiwidjaja, G. Tetrahedron Lett. 1991, 32, 1299] and phosophonamides [(j) Fernández, I.; Ortiz, F. L.; Tejerina, B.; Granda, S. G. Org. Lett. 2001, 3, 1339; (k) Gómez, G. R.; Ortiz, F. L. Synlett 2002, 781] undergo anionic cyclizations with loss of aromaticity. For a review, see: Ref. 3a.
27. Hammerschmidt F., Hanninger A. Chem. Ber. 128:1995;823.
28. Aldol products 4d and 6d were formed as single diastereoisomers: relative stereochemistry at the hydroxyl bearing centre was assigned by analogy with a similar reaction. See: Ref. 5a.
29. HPLC on the Regis Whelk-O1® chiral stationary phase.
30. We previously demonstrated stereospecificity in the dearomatizing cyclization of a secondary organolithium. See: Clayden J., Menet C.J., Mansfield D.J. Chem. Commun. 2002;38.
31. Invertive electrophilic substitution at benzyllithiums is precedented, but not invertive deprotonation (see Refs. 2 and 3): Ockham's razor (Hoffmann, R. Bull. Soc. Chim. Fr. 1996, 133, 117) leads us to discount a double inversion mechanism.
32. Bragg R.A., Clayden J. Tetrahedron Lett. 40:1999;8323.
33. Bragg R.A., Clayden J. Tetrahedron Lett. 40:1999;8327.
34. Marshall J.A., Lebreton J. J. Am. Chem. Soc. 110:1988;2925.
35. Overberger C.G., Marullo N.P., Hiskey R.G. J. Am. Chem. Soc. 81:1959;1517.
36. Bragg R.A., Clayden J., Menet C.J. Tetrahedron Lett. 43:2002;1955.
37. 3I.
38. See Ref. 14 and Bull S.D., Davies S.G., Kelly P.M., Gianotti M., Smith A.D. J. Chem. Soc., Perkin Trans. 1. 2001;3106.
39. Parsons A.F. Tetrahedron. 52:1996;4149.
40. Clayden J., Tchabanenko K. Chem. Commun. 2000;317.
41. Clayden J., Menet C.J., Tchabanenko K. Tetrahedron. 58:2002;4727.
42. Ahmed A., Bragg R.A., Clayden J., Tchabanenko K. Tetrahedron Lett. 42:2001;3407.
43. Bragg R.A., Clayden J., Bladon M., Ichihara O. Tetrahedron Lett. 42:2001;3411.
44. (a) Carlsen P.H., Katsuki T., Martín V.S., Sharpless K.B. J. Org. Chem. 46:1981;3936
45. (b) Shioiri, T.; Matsuura, F.; Hamada, Y. Pure Appl. Chem. 1994, 66, 2151. In our synthesis of (-)-kainic acid (Ref. 18b) we used a meta-methoxy substituent to facilitate oxidation
46. The regioselectivity appears to be a conformational effect involving the nearby methyl group. See: Ref. 18.
47. Collado I., Ezquerra J., Mateo A.I., Rubio A. J. Org. Chem. 63:1998;1995.