Efficient and Z-selective cross-metathesis of conjugated enynes

Organic Letters

Volumn 6, Issue 12, 2004, Pages 2035-2038

  Hansen, Eric C ^a   Lee, Daesung ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE; ALKYNE DERIVATIVE; ALLYL COMPOUND;

ARTICLE; CATALYST; CHEMICAL REACTION; CONJUGATION;

EID: 3042792529     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol049378i     Document Type: Article

References (43)

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29. Mechanistically, conjugated alkenyl alkylidenes are involved in all enyne methathesis processes. For recent examples of ring closing metathesis reactions employing conjugated dienes as starting materials to generate the putative conjugated alkenyl alkylidenes as intermediates, see: (a) Frederique, R.; Claire, V.; Laurent, E.; Laurence, G. Org. Lett. 2003, 5, 2007. (b) Wang, X.; Porco, J. A., Jr. J. Am. Chem. Soc. 2003, 125, 6040. (c) Evano, G.; Schaus, J. V.; Panek, J. S. Org. Lett. 2004, 6, 525.
30. Mechanistically, conjugated alkenyl alkylidenes are involved in all enyne methathesis processes. For recent examples of ring closing metathesis reactions employing conjugated dienes as starting materials to generate the putative conjugated alkenyl alkylidenes as intermediates, see: (a) Frederique, R.; Claire, V.; Laurent, E.; Laurence, G. Org. Lett. 2003, 5, 2007. (b) Wang, X.; Porco, J. A., Jr. J. Am. Chem. Soc. 2003, 125, 6040. (c) Evano, G.; Schaus, J. V.; Panek, J. S. Org. Lett. 2004, 6, 525.
31. Mechanistically, conjugated alkenyl alkylidenes are involved in all enyne methathesis processes. For recent examples of ring closing metathesis reactions employing conjugated dienes as starting materials to generate the putative conjugated alkenyl alkylidenes as intermediates, see: (a) Frederique, R.; Claire, V.; Laurent, E.; Laurence, G. Org. Lett. 2003, 5, 2007. (b) Wang, X.; Porco, J. A., Jr. J. Am. Chem. Soc. 2003, 125, 6040. (c) Evano, G.; Schaus, J. V.; Panek, J. S. Org. Lett. 2004, 6, 525.
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34. The Z-selective cross metathesis of acrylonitrile, see: (a) Crowe, W. E.; Goldberg D. R. J. Am. Chem. Soc. 1995, 117, 5162. (b) Randle, S.; Gessler, S.; Wakamatsu, H.; Blechert, S. Synlett 2001, 430.
35. A similar strategy to generate alkylidene at a less reactive site by the initiation from the remote site followed by intramolecular delivery of the catalyst has been pursued by Hoye and co-workers and termed "Relay Metathesis". See: Zhao, H. Ph.D. Thesis, University of Minnesota, 2001. Lange, B. S. Abstracts of Papers, 227th National Meeting of the American Chemical Society, Anaheim, CA; American Chemical Society: Washington, DC, 2004; CHED 899. See also ref 12b and Robinson, J.; Piscopio, A. D. Abstracts of Papers, 226th National Meeting of the American Chemical Society, New York, NY; American Chemical Society: Washington, DC, September, 2003.
36. A similar strategy to generate alkylidene at a less reactive site by the initiation from the remote site followed by intramolecular delivery of the catalyst has been pursued by Hoye and co-workers and termed "Relay Metathesis". See: Zhao, H. Ph.D. Thesis, University of Minnesota, 2001. Lange, B. S. Abstracts of Papers, 227th National Meeting of the American Chemical Society, Anaheim, CA; American Chemical Society: Washington, DC, 2004; CHED 899. See also ref 12b and Robinson, J.; Piscopio, A. D. Abstracts of Papers, 226th National Meeting of the American Chemical Society, New York, NY; American Chemical Society: Washington, DC, September, 2003.
37. A similar strategy to generate alkylidene at a less reactive site by the initiation from the remote site followed by intramolecular delivery of the catalyst has been pursued by Hoye and co-workers and termed "Relay Metathesis". See: Zhao, H. Ph.D. Thesis, University of Minnesota, 2001. Lange, B. S. Abstracts of Papers, 227th National Meeting of the American Chemical Society, Anaheim, CA; American Chemical Society: Washington, DC, 2004; CHED 899. See also ref 12b and Robinson, J.; Piscopio, A. D. Abstracts of Papers, 226th National Meeting of the American Chemical Society, New York, NY; American Chemical Society: Washington, DC, September, 2003.
38. The involvement of a slow initiating methylidene in the former could also result in inefficient turn over.
39. For the preparation of 5, see the Supporting Information.
40. The formation of cross-coupled products 14e,f is a strong indication of the preferential initiation of the metathesis at the alkene moiety over the alkyne.
41. (a) Ulman, M.; Belderrain, T. R.; Grubbs, R. H. Tetrahedron Lett. 2000, 41, 4689.
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43. Although a stoichiometric amount of catalyst was used, only a small fraction underwent initiation to catalyze the reaction of 19 and 20. Therefore, only a small amount of styrene was observed by NMR.