Organotin hydride-catalyzed conjugate reduction of α,β-unsaturated ketones

Journal of Organic Chemistry

Volumn 61, Issue 19, 1996, Pages 6751-6752

  Hays, David S ^a   Scholl, Matthias ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001639833     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo960846e     Document Type: Article

References (39)

1. Pereyre, M.; Quintard, J.-P.; Rahm, A. Tin in Organic Synthesis; Butterworths: Boston, 1987.
2. 3SnH, see: (a) Neumann, W. P. Synthesis 1987, 665-683. (b) RajanBabu, T. V. In Encyclopedia of Reagents for Organic Synthesis; Paquette, L. A., Ed.; Wiley: New York, 1995.
3. 3SnH, see: (a) Neumann, W. P. Synthesis 1987, 665-683. (b) RajanBabu, T. V. In Encyclopedia of Reagents for Organic Synthesis; Paquette, L. A., Ed.; Wiley: New York, 1995.
4. For leading references to radical chemistry, see:(a) Hart, D. J. Science 1984, 223, 883-887. (b) Giese, B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds; Pergamon: New York, 1986. (c) Curran, D. P. Synthesis 1988, 417-439, 489-513. (d) Regitz, M.; Giese, B. Houben-Weyl, Methoden der Organischen Chemie; Georg Thieme Verlag: Stuttgart, 1989. (e) Motherwell, W. B.; Crich, D. Free Radical Chain Reactions in Organic Synthesis; Academic: New York, 1992. (f) Curran, D. P.; Porter, N. A.; Giese, B. Stereochemistry of Radical Reactions; VCH: New York, 1996.
5. For leading references to radical chemistry, see:(a) Hart, D. J. Science 1984, 223, 883-887. (b) Giese, B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds; Pergamon: New York, 1986. (c) Curran, D. P. Synthesis 1988, 417-439, 489-513. (d) Regitz, M.; Giese, B. Houben-Weyl, Methoden der Organischen Chemie; Georg Thieme Verlag: Stuttgart, 1989. (e) Motherwell, W. B.; Crich, D. Free Radical Chain Reactions in Organic Synthesis; Academic: New York, 1992. (f) Curran, D. P.; Porter, N. A.; Giese, B. Stereochemistry of Radical Reactions; VCH: New York, 1996.
6. For leading references to radical chemistry, see:(a) Hart, D. J. Science 1984, 223, 883-887. (b) Giese, B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds; Pergamon: New York, 1986. (c) Curran, D. P. Synthesis 1988, 417-439, 489-513. (d) Regitz, M.; Giese, B. Houben-Weyl, Methoden der Organischen Chemie; Georg Thieme Verlag: Stuttgart, 1989. (e) Motherwell, W. B.; Crich, D. Free Radical Chain Reactions in Organic Synthesis; Academic: New York, 1992. (f) Curran, D. P.; Porter, N. A.; Giese, B. Stereochemistry of Radical Reactions; VCH: New York, 1996.
7. For leading references to radical chemistry, see:(a) Hart, D. J. Science 1984, 223, 883-887. (b) Giese, B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds; Pergamon: New York, 1986. (c) Curran, D. P. Synthesis 1988, 417-439, 489-513. (d) Regitz, M.; Giese, B. Houben-Weyl, Methoden der Organischen Chemie; Georg Thieme Verlag: Stuttgart, 1989. (e) Motherwell, W. B.; Crich, D. Free Radical Chain Reactions in Organic Synthesis; Academic: New York, 1992. (f) Curran, D. P.; Porter, N. A.; Giese, B. Stereochemistry of Radical Reactions; VCH: New York, 1996.
8. For leading references to radical chemistry, see:(a) Hart, D. J. Science 1984, 223, 883-887. (b) Giese, B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds; Pergamon: New York, 1986. (c) Curran, D. P. Synthesis 1988, 417-439, 489-513. (d) Regitz, M.; Giese, B. Houben-Weyl, Methoden der Organischen Chemie; Georg Thieme Verlag: Stuttgart, 1989. (e) Motherwell, W. B.; Crich, D. Free Radical Chain Reactions in Organic Synthesis; Academic: New York, 1992. (f) Curran, D. P.; Porter, N. A.; Giese, B. Stereochemistry of Radical Reactions; VCH: New York, 1996.
9. For leading references to radical chemistry, see:(a) Hart, D. J. Science 1984, 223, 883-887. (b) Giese, B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds; Pergamon: New York, 1986. (c) Curran, D. P. Synthesis 1988, 417-439, 489-513. (d) Regitz, M.; Giese, B. Houben-Weyl, Methoden der Organischen Chemie; Georg Thieme Verlag: Stuttgart, 1989. (e) Motherwell, W. B.; Crich, D. Free Radical Chain Reactions in Organic Synthesis; Academic: New York, 1992. (f) Curran, D. P.; Porter, N. A.; Giese, B. Stereochemistry of Radical Reactions; VCH: New York, 1996.
10. Boyer, I. J. Toxicology 1989, 55, 253-298.
11. (a) Chatgilialoglu, C. Ace. Chem. Res. 1992, 25, 188-194.
12. (b) Giese, B.; Dickhaut, J. In Encyclopedia of Reagents for Organic Synthesis; Paquette, L. A., Ed.; Wiley: New York, 1995.
13. Barton, D. H. R.; Jang, D. O.; Jaszberenyi, J. C. J. Org. Chem. 1993, 58, 6838-6842.
14. For example, see: Ballestri, M.; Chatgilialoglu, C.; Lucarini, M.; Pedulli, G. F. J. Org. Chem. 1992, 57, 948-952. See also ref 5a.
15. For example, see: (a) Apeloig, Y.; Nakash, M. J. Am. Chem. Soc. 1994, 116, 10781-10782. (b) Lee, E.; Park, C. M.; Yun, J. S. J. Am. Chem. Soc. 1995, 117, 8017-8018.
16. For example, see: (a) Apeloig, Y.; Nakash, M. J. Am. Chem. Soc. 1994, 116, 10781-10782. (b) Lee, E.; Park, C. M.; Yun, J. S. J. Am. Chem. Soc. 1995, 117, 8017-8018.
17. 3SnH-catalyzed radical processes, see: (a) Corey, E. J.; Suggs, J. W. J. Org. Chem. 1975, 40, 2554-2555. (b) Stork, G.; Sher, P. M. J. Am. Chem. Soc. 1986, 108, 303-304.
18. 3SnH-catalyzed radical processes, see: (a) Corey, E. J.; Suggs, J. W. J. Org. Chem. 1975, 40, 2554-2555. (b) Stork, G.; Sher, P. M. J. Am. Chem. Soc. 1986, 108, 303-304.
19. For applications of this approach to polar chemistry, see: (a) Tin hydride: Lipowitz, J.; Bowman, S. A. J. Org. Chem. 1973, 38, 162-165. Vedejs, E.; Duncan, S. M.; Haight, A. R. J. Org. Chem. 1993, 58, 3046-3050. (b) Tin cyanide: Scholl, M.; Fu, G. C. J. Org. Chem. 1994, 59, 7178-7179. Scholl, M.; Lim, C.-K.; Fu, G. C. J. Org. Chem. 1995, 60, 6229-6231.
20. For applications of this approach to polar chemistry, see: (a) Tin hydride: Lipowitz, J.; Bowman, S. A. J. Org. Chem. 1973, 38, 162-165. Vedejs, E.; Duncan, S. M.; Haight, A. R. J. Org. Chem. 1993, 58, 3046-3050. (b) Tin cyanide: Scholl, M.; Fu, G. C. J. Org. Chem. 1994, 59, 7178-7179. Scholl, M.; Lim, C.-K.; Fu, G. C. J. Org. Chem. 1995, 60, 6229-6231.
21. For applications of this approach to polar chemistry, see: (a) Tin hydride: Lipowitz, J.; Bowman, S. A. J. Org. Chem. 1973, 38, 162-165. Vedejs, E.; Duncan, S. M.; Haight, A. R. J. Org. Chem. 1993, 58, 3046-3050. (b) Tin cyanide: Scholl, M.; Fu, G. C. J. Org. Chem. 1994, 59, 7178-7179. Scholl, M.; Lim, C.-K.; Fu, G. C. J. Org. Chem. 1995, 60, 6229-6231.
22. For applications of this approach to polar chemistry, see: (a) Tin hydride: Lipowitz, J.; Bowman, S. A. J. Org. Chem. 1973, 38, 162-165. Vedejs, E.; Duncan, S. M.; Haight, A. R. J. Org. Chem. 1993, 58, 3046-3050. (b) Tin cyanide: Scholl, M.; Fu, G. C. J. Org. Chem. 1994, 59, 7178-7179. Scholl, M.; Lim, C.-K.; Fu, G. C. J. Org. Chem. 1995, 60, 6229-6231.
23. (a) For a suggestion that radical-mediated reactions might be susceptible to this strategy, see: Lipowitz, J.; Bowman, S. A. Aldrichim. Acta 1973, 6, 1-6.
24. (b) For an application of this approach to radical chemistry, see: Hays, D. S.; Fu, G. C. J. Org. Chem. 1996, 61, 4-5.
25. For other methods for effecting the conjugate reduction of enones, see:(a) Larock, R. C. Comprehensive Organic Transformations; VCH: New York, 1989; pp 9-12. (b) Parkes, K. E. B.; Richardson, S. K. In Comprehensive Organic Functional Group Transformations; Katritzky, A. R., Meth-Cohn, O., Rees, C. W., Eds.; Pergamon: New York, 1995; Vol. 3, pp 127-128. (c) Keinan, E.; Greenspoon, N. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon: New York, 1991; Vol. 8, Chapter 3.5.
26. For other methods for effecting the conjugate reduction of enones, see:(a) Larock, R. C. Comprehensive Organic Transformations; VCH: New York, 1989; pp 9-12. (b) Parkes, K. E. B.; Richardson, S. K. In Comprehensive Organic Functional Group Transformations; Katritzky, A. R., Meth-Cohn, O., Rees, C. W., Eds.; Pergamon: New York, 1995; Vol. 3, pp 127-128. (c) Keinan, E.; Greenspoon, N. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon: New York, 1991; Vol. 8, Chapter 3.5.
27. For other methods for effecting the conjugate reduction of enones, see:(a) Larock, R. C. Comprehensive Organic Transformations; VCH: New York, 1989; pp 9-12. (b) Parkes, K. E. B.; Richardson, S. K. In Comprehensive Organic Functional Group Transformations; Katritzky, A. R., Meth-Cohn, O., Rees, C. W., Eds.; Pergamon: New York, 1995; Vol. 3, pp 127-128. (c) Keinan, E.; Greenspoon, N. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon: New York, 1991; Vol. 8, Chapter 3.5.
28. (a) Pereyre, M.; Valade, J. Compt. Rend. 1965, 260, 581-584.
29. (b) Pereyre, M.; Valade, J. Bull. Soc. Chim. Fr. 1967, 1928-1936. For an overview, see ref 1.
30. For an application of this process in natural products chemistry, see: Laurent, H.; Esperling, P.; Baude, G. Liebigs Ann. Chem. 1983, 1996-1999.
31. Tin enolates exist as a mixture of interconverting tautomers in which the tin is bound either to oxygen or to carbon. For simplicity, we have illustrated the oxygen-bound tautomer in eq 1 and Scheme 1. See: (a) Pereyre, M.; Bellegarde, B.; Mendelsohn, J.; Valade, J. J. Organomet. Chem. 1968, 11, 97-110. (b) Lutsenko, I. F.; Baukov, Y. I.; Belavin, I. Y. J. Organomet. Chem. 1970, 24, 359-369.
32. Tin enolates exist as a mixture of interconverting tautomers in which the tin is bound either to oxygen or to carbon. For simplicity, we have illustrated the oxygen-bound tautomer in eq 1 and Scheme 1. See: (a) Pereyre, M.; Bellegarde, B.; Mendelsohn, J.; Valade, J. J. Organomet. Chem. 1968, 11, 97-110. (b) Lutsenko, I. F.; Baukov, Y. I.; Belavin, I. Y. J. Organomet. Chem. 1970, 24, 359-369.
33. (a) Bellegarde, B.; Pereyre, M.; Valade, J. Bull. Soc. Chim. Fr. 1967, 746-747.
34. (b) Bellegarde, B.; Pereyre, M.; Valade, J. Bull. Soc. Chim. Fr. 1967, 3082-3083.
35. A mixture of silyl enol ethers (bearing zero to two hydrogens on silicon) is probably formed.
36. Lower yields are observed when polymethylhydrosiloxane is employed as the stoichiometric reductant.
37. Because the enone product illustrated in entry 6 (Table 1) is not revealed until hydrolysis of the initially formed silyl enol ether occurs (Scheme 1), only one of the two carbon-carbon double bonds of trans,trans-dibenzylideneacetone is reduced.
38. (a) Ojima, I.; Kogure, T.; Nagai, Y. Tetrahedron Lett. 1972, 5035-5088.
39. (b) Reference 12.