Stereoselective Preparation of 1-Siloxy-1-alkenylcopper Species by 1,2-Csp2-to-O Silyl Migration of Acylsilanes

• Published in: Journal of the American Chemical Society Vol. 128; no. 44; pp. 14268 - 14269
• Main Authors: Tsubouchi, Akira, Onishi, Kotaro, Takeda, Takeshi
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 08-11-2006
• Subjects: Chemistry; Exact sciences and technology; General and physical chemistry; Stereoselectivity; Chemical rearrangement; Copper Organic compounds; Organic siloxane; Organic silane; Chemical synthesis; Ethylenic compound
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja0658822

1-Siloxy-1-alkenylcopper species were generated by 1,2-Csp2-to-O silyl migration of the copper enolates of acyltriphenylsilanes. The alkenylcopper species reacted with methyl, benzyl, allylic, and tributylstannyl halides to give geometrically pure (Z)-enol silyl ethers. In the presence of Pd(0) catalyst, the cross-coupling of the alkenyl copper species with aryl and alkenyl iodides also proceeded to give the (Z)-enol silyl ethers with high stereoselectivity.