A novel use of the anions of Fischer-type carbene complexes as alkenyl metallic species

Tetrahedron

Volumn 56, Issue 28, 2000, Pages 4907-4915

  Fuchibe, Kohei ^a   Iwasawa, Nobuharu ^b  

^a UNIVERSITY OF TOKYO   (Japan)

^b TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

Alkylcerium reagents; Fischer type carbene complexes; Iodine oxidation; Lithium enolates; Methoxycarbonylation

Indexed keywords

ALKENYL GROUP; ANION; CARBENE; METAL COMPLEX;

CHEMICAL STRUCTURE; COMPLEX FORMATION; CONFERENCE PAPER; MOLECULAR INTERACTION; OXIDATION; PRIORITY JOURNAL; PROTON TRANSPORT; SYNTHESIS;

EID: 0034617061     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(00)00205-2     Document Type: Conference Paper

References (35)

1. Fischer E.O., Maasböl A. Angew. Chem., Int. Ed. Engl. 3:1964;580.
2. For review, see: (a) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1984, 23, 587. (b) Brown, F. J. Prog. Inorg. Chem. 1980, 27, 1. (c) Wulff, W. D. In Comprehensive Organic Synthesis; Trost, B. M., Flemming, I., Eds.; Pergamon: New York, 1991; Vol. 5, p 1065. (d) Wulff, W. D. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, 1995; Vol. 12, p 469. (e) Doyle, M. P. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, 1995; Vol. 12, p 387. (f) Hegedus, L. S. Tetrahedron, 1997, 53, 4105. (g) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1975, 14, 644.
3. For review, see: (a) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1984, 23, 587. (b) Brown, F. J. Prog. Inorg. Chem. 1980, 27, 1. (c) Wulff, W. D. In Comprehensive Organic Synthesis; Trost, B. M., Flemming, I., Eds.; Pergamon: New York, 1991; Vol. 5, p 1065. (d) Wulff, W. D. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, 1995; Vol. 12, p 469. (e) Doyle, M. P. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, 1995; Vol. 12, p 387. (f) Hegedus, L. S. Tetrahedron, 1997, 53, 4105. (g) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1975, 14, 644.
4. For review, see: (a) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1984, 23, 587. (b) Brown, F. J. Prog. Inorg. Chem. 1980, 27, 1. (c) Wulff, W. D. In Comprehensive Organic Synthesis; Trost, B. M., Flemming, I., Eds.; Pergamon: New York, 1991; Vol. 5, p 1065. (d) Wulff, W. D. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, 1995; Vol. 12, p 469. (e) Doyle, M. P. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, 1995; Vol. 12, p 387. (f) Hegedus, L. S. Tetrahedron, 1997, 53, 4105. (g) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1975, 14, 644.
5. For review, see: (a) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1984, 23, 587. (b) Brown, F. J. Prog. Inorg. Chem. 1980, 27, 1. (c) Wulff, W. D. In Comprehensive Organic Synthesis; Trost, B. M., Flemming, I., Eds.; Pergamon: New York, 1991; Vol. 5, p 1065. (d) Wulff, W. D. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, 1995; Vol. 12, p 469. (e) Doyle, M. P. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, 1995; Vol. 12, p 387. (f) Hegedus, L. S. Tetrahedron, 1997, 53, 4105. (g) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1975, 14, 644.
6. For review, see: (a) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1984, 23, 587. (b) Brown, F. J. Prog. Inorg. Chem. 1980, 27, 1. (c) Wulff, W. D. In Comprehensive Organic Synthesis; Trost, B. M., Flemming, I., Eds.; Pergamon: New York, 1991; Vol. 5, p 1065. (d) Wulff, W. D. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, 1995; Vol. 12, p 469. (e) Doyle, M. P. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, 1995; Vol. 12, p 387. (f) Hegedus, L. S. Tetrahedron, 1997, 53, 4105. (g) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1975, 14, 644.
7. For review, see: (a) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1984, 23, 587. (b) Brown, F. J. Prog. Inorg. Chem. 1980, 27, 1. (c) Wulff, W. D. In Comprehensive Organic Synthesis; Trost, B. M., Flemming, I., Eds.; Pergamon: New York, 1991; Vol. 5, p 1065. (d) Wulff, W. D. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, 1995; Vol. 12, p 469. (e) Doyle, M. P. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, 1995; Vol. 12, p 387. (f) Hegedus, L. S. Tetrahedron, 1997, 53, 4105. (g) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1975, 14, 644.
8. For review, see: (a) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1984, 23, 587. (b) Brown, F. J. Prog. Inorg. Chem. 1980, 27, 1. (c) Wulff, W. D. In Comprehensive Organic Synthesis; Trost, B. M., Flemming, I., Eds.; Pergamon: New York, 1991; Vol. 5, p 1065. (d) Wulff, W. D. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, 1995; Vol. 12, p 469. (e) Doyle, M. P. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, 1995; Vol. 12, p 387. (f) Hegedus, L. S. Tetrahedron, 1997, 53, 4105. (g) Dötz, K. H. Angew. Chem., Int. Ed. Engl. 1975, 14, 644.
9. For example, the pKa of the methyl carbene complex of chromium (R=H in Eq. (1)) is 8 (in THF) and 12 (in water). See: Casey, C. P.; Anderson, R. L. J. Am. Chem. Soc. 1974, 96, 1230; Gandler, J. R.; Bernasconi, C. F.; Sun, W. Organometallics 1989, 8, 2282.
10. For example, the pKa of the methyl carbene complex of chromium (R=H in Eq. (1)) is 8 (in THF) and 12 (in water). See: Casey, C. P.; Anderson, R. L. J. Am. Chem. Soc. 1974, 96, 1230; Gandler, J. R.; Bernasconi, C. F.; Sun, W. Organometallics 1989, 8, 2282.
11. For alkylation, see: Xu, Y.-C.; Wulff, W. D. J. Org. Chem. 1987, 52, 3263. For aldol-type addition, see: Wulff, W. D.; Gilbertson, S. R. J. Am. Chem. Soc. 1985, 107, 503; Aumann, R.; Heinen, H. Chem. Ber. 1987, 120, 537.
12. For alkylation, see: Xu, Y.-C.; Wulff, W. D. J. Org. Chem. 1987, 52, 3263. For aldol-type addition, see: Wulff, W. D.; Gilbertson, S. R. J. Am. Chem. Soc. 1985, 107, 503; Aumann, R.; Heinen, H. Chem. Ber. 1987, 120, 537.
13. For alkylation, see: Xu, Y.-C.; Wulff, W. D. J. Org. Chem. 1987, 52, 3263. For aldol-type addition, see: Wulff, W. D.; Gilbertson, S. R. J. Am. Chem. Soc. 1985, 107, 503; Aumann, R.; Heinen, H. Chem. Ber. 1987, 120, 537.
14. (a) For example, see: Chan, K. S.; Yeung, M. L.; Chan, W.-K.; Wang, R.-J.; Mak, T. C. W. J. Org. Chem. 1995, 60, 1741.
15. (b) Casey, C. P.; Brunsvold, W. R. J. Organomet. Chem. 1975, 102, 175.
16. For example, see: Wulff, W. D.; Yang, D.C. J. Am. Chem. Soc. 1983, 105, 6726.
17. Iwasawa N., Maeyama K., Saitou M. J. Am. Chem. Soc. 119:1997;1486.
18. Iwasawa, N.; Ochiai, T.; Maeyama, K. J. Org. Chem. 1998, 63, 3164. See also: Iwasawa, N.; Ochiai, T.; Maeyama, K. Organometallics 1997, 16, 5137.
19. Iwasawa, N.; Ochiai, T.; Maeyama, K. J. Org. Chem. 1998, 63, 3164. See also: Iwasawa, N.; Ochiai, T.; Maeyama, K. Organometallics 1997, 16, 5137.
20. Iwasawa N., Fuchibe K. Chem. Lett. 1998;1149.
21. When butyllithium was employed as base, it partly underwent nucleophilic addition to the carbene carbon to yield 5-nonanone in about 40% yield after iodine-oxidation.
22. The stereochemistry of the double bond of the unsaturated ester 5 was determined by the measurement of differential NOE of the allylic alcohol obtained by DIBAL reduction of 5.
23. It should be noted that the anionic species 4 is not protonated by methanol under these conditions.
24. 11.
25. This iodide 12 was unstable and its stereochemistry was determined immediately after separation by preparative TLC. The stereochemistry of alkenyl iodide 12 was determined by the coupling constant (6.9 Hz) between the vicinal olefinic protons of the alkenyl ether prepared by lithiation and protonation of 12.
26. (a) Nakamura, E.; Tanaka, K.; Fujimura, T.; Aoki, S.; Willard, P. G. J. Am. Chem. Soc. 1993, 115, 9015.
27. (b) Shi, Y.; Wulff, W. D. J. Org. Chem. 1994, 59, 5122.
28. (c) Casey, C. P.; Brunsvold, W. R. Inorg. Chem. 1977, 16, 391.
29. 11.
30. The stereochemistries of the other products in Table 1 were all assigned to be Z from the chemical shifts of the olefinic protons which were all distributed between 6.17-6.29 ppm. These values are close to that of 11 (6.08 ppm, established to have Z configuration), and far from the value of 5 (5.25 ppm, established to have E configuration).
31. The stereochemistries of the double bond were determined in a similar manner to the cases of isobutenyl carbene complex 15. All the products consist of 4 isomers. Two of them have olefinic protons between 4.91-5.39 ppm, and the others are distributed between 6.04-6.43 ppm. The former are assigned to have E configuration, and the latter to have Z configuration.
32. There are several specific examples of the 1,4-addition of organolithium reagents to α,β-unsaturated carbene complexes, see: Barluenga, J.; Trabanco, A. A.; Flórez, J.; García-Granda, S.; Martín, E. J. Am. Chem. Soc. 1996, 118, 13099; Barluenga, J.; Montserrat, J. M.; García-Granda, S.; Martín, E. Chem. Eur. J. 1995, 1, 236, and references are cited therein.
33. There are several specific examples of the 1,4-addition of organolithium reagents to α,β-unsaturated carbene complexes, see: Barluenga, J.; Trabanco, A. A.; Flórez, J.; García-Granda, S.; Martín, E. J. Am. Chem. Soc. 1996, 118, 13099; Barluenga, J.; Montserrat, J. M.; García-Granda, S.; Martín, E. Chem. Eur. J. 1995, 1, 236, and references are cited therein.
34. Imamoto T., Takiyama N., Nakamura K., Hatajima T., Kamiya Y. J. Am. Chem. Soc. 111:1989;4392.
35. 6, followed by methylation using methyl triflate. See: Wulff, W. D.; Bauta, W. E.; Kaesler, R. W.; Lankford, P. J.; Miller, R. A.; Murray, C. K.; Yang, D. C. J. Am. Chem. Soc. 1990, 112, 3642.