Iron-Catalyzed anti-Selective Carbosilylation of Internal Alkynes.

Autor: Iwamoto T; International Research Center for Elements Sciencem Institute for Chemical Research (ICR), Kyoto University, Uji, Kyoto, 611-0011, Japan.; Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto, 615-8510, Japan.; CREST Japan, Science and Technology Agency (JST), Japan., Nishikori T; International Research Center for Elements Sciencem Institute for Chemical Research (ICR), Kyoto University, Uji, Kyoto, 611-0011, Japan.; Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto, 615-8510, Japan., Nakagawa N; International Research Center for Elements Sciencem Institute for Chemical Research (ICR), Kyoto University, Uji, Kyoto, 611-0011, Japan.; Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto, 615-8510, Japan., Takaya H; International Research Center for Elements Sciencem Institute for Chemical Research (ICR), Kyoto University, Uji, Kyoto, 611-0011, Japan.; Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto, 615-8510, Japan., Nakamura M; International Research Center for Elements Sciencem Institute for Chemical Research (ICR), Kyoto University, Uji, Kyoto, 611-0011, Japan.; Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto, 615-8510, Japan.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2017 Oct 16; Vol. 56 (43), pp. 13298-13301. Date of Electronic Publication: 2017 Sep 19.
DOI: 10.1002/anie.201706333
Abstrakt: Reported is the anti-selective carbosilylation of internal alkynes with silylborane and alkyl halides using a FeBr 2 /DPPE catalyst system. The iron catalyst allows simultaneous introduction of a carbon electrophile and a silicon nucleophile to simple internal alkynes, including diaryl-, dialkyl-, and aryl/alkyl-substituted alkynes, in a highly stereoselective manner. Alkyl halides are applicable as the electrophiles, thereby enabling the synthesis of a variety of tetrasubstituted alkenylsilanes. In addition, syn-selective carbosilylation was achieved through stereoswitching, by using a silylborane having oxygen functionality on the silyl group. This novel iron-catalyzed carbosilylation is a useful tool for expedient synthesis of stereodefined multisubstituted olefins, a fundamental structural motif in organic chemistry.
(© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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