Preparation of allylsilanes via cross-metathesis

Tetrahedron Letters

Volumn 37, Issue 13, 1996, Pages 2117-2120

  Crowe, William E ^a   Goldberg, Daniel R ^a   Zhang, Zhijia J ^a  

^a EMORY UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYL COMPOUND; SILANE DERIVATIVE;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS; TECHNIQUE;

EID: 0029881520     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)00230-4     Document Type: Article

References (27)

1. Reviews: (a) Fleming, I. In Comprehensive Organic Synthesis; B. M. Trost, Ed.; Pergamon Press: Oxford, 1989; Vol. 2; pp 563-593.
2. (b) Chan, T. H.; Wang, D. Chem. Rev. 1992, 92, 995-1006.
3. (c) Yamamoto, Y.; Asao, N. Chem. Rev. 1993, 93, 2207-2293.
4. (d) Sarkar, T. K. Synthesis 1990, 1101-1111.
5. (e) Sarkar, T. K. Synthesis 1990, 969-983.
6. (a) Seyferth, D.; Wursthorn, K. R.; Mammarella, R. E. J. Org. Chem. 1977, 42, 3104.
7. (b) Seyferth, D.; Wursthorn, K. R.; Lim, T. F. O.; Sepelak, D. J. J. Organomet. Chem. 1979, 181, 293-304.
8. (c) Fleming, I.; Paterson, I. Synthesis 1979, 446-448.
9. A yield-limiting side reaction which sometimes occurs is: equation presented See: (a) Tsukamoto, M.; Iio, H.; Tokoroyama, T. Tetrahedron Lett. 1985, 26, 4471-4474.
10. (b) Tsukamoto, M.; Iio, H.; Tokoroyama, T. J. Chem. Soc., Chem. Commun. 1986, 880-882.
11. (c) Hughes, L. R.; Schmid, R.; Johnson, W. S. Bioorg. Chem. 1979, 8, 513-518.
12. Crowe, W. E.; Zhang, Z. J. J Am. Chem. Soc. 1993, 115, 10998-10999.
13. Crowe, W. E.; Goldberg, D. R. J. Am. Chem. Soc. 1995, 117, 5162-5163.
14. (a) Murdzek, J. S.; Schrock, R. R. Organometallics 1987, 6, 1373-1374.
15. (b) Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; O'Regan, M. B. J. Am. Chem. Soc. 1990, 112, 3875-3886.
16. (c) Fox, H. H.; Yap, K. B.; Robbins, J.; Cai, S.; Schrock, R. R. Inorg. Chem. 1992, 31, 2287-2289.
17. 3 (hexane eluent) to provide 116 mg (83%) of trimethyl[3-(4-methylphenyl)-2-propenyl]silane as a clear, colorless liquid. A similar reaction run with 5.0 g (42 mmol) of 4-methylstyrene, 9.66 g (84 mmol) of allyltrimethylsilane, 324 mg (1 mol%) of catalyst afforded 7.8 g (89%) of trimethyl[3-(4-methylphenyl)-2-propenyl]silane and 0.44g (9%) of unreacted 4-methylstyrene.
18. 13C NMR, and IR spectroscopy and gave satisfactory combustion analysis and/or high-resolution mass spectrometric data.
19. DME has been shown to stabilize methylene complexes formed as reactive intermediates in and products of molybdenum-catalyzed olefin metathesis reactions: (a) Fox, H. H.; Lee, J. K.; Park, L. Y.; Schrock, R. R. Organometallics 1993, 12, 759-768.
20. (b) Fox, H. H.; Schrock, R. R.; Odell, R. Organometallics 1994, 13, 635-639.
21. 9 formed as reactive intermediate in the coupling reaction.
22. Gupta, A. D.; Dev, S. J. J. Chromatogr. 1963, 12, 189-195.
23. Alkylidene reactivity has been shown to be strongly dependent on the size of the alkylidene substituent. See, for example: (a) Schrock, R. R.; DePue, R. T.; Feldman, J.; Schaverien, C. J.; Dewan, J. C.; Liu, A. H. J. Am. Chem. Soc. 1988, 110, 1423-35.
24. (b) Feldman, J. Ph.D. Thesis, Massachusetts Institute of Technology, 1989; pp 59-63.
25. (c) Schlund, R.; Schrock, R. R.; Crowe, W. E. J Am. Chem. Soc. 1989, 111, 8004.
26. This probably reflects a counterbalance of increased electron-richness (increasing reactivity) and greater steric bulk (decreasing reactivity) of allyltrimethylsilane compared to a small, alkyl-substituted olefin.
27. Preliminary experiments show that allyltributylstannane can be selectively cross-metathesized with substituted styrenes. Crowe, W. E.; Goldberg, D. R.; Zhang, Z. J, work in progress.