Copper(I)-Catalyzed Enantioselective Synthesis of 伪-Chiral Linear or Carbocyclic (E)-(纬-Alkoxyallyl)boronates
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- 作者：Eiji Yamamoto ; Yuta Takenouchi ; Taichi Ozaki ; Takanori Miya ; Hajime Ito
- 刊名：Journal of the American Chemical Society
- 出版年：2014
- 出版时间：November 26, 2014
- 年：2014
- 卷：136
- 期：47
- 页码：16515-16521
- 全文大小：572K
- ISSN：1520-5126
文摘
A new method has been developed for the catalytic asymmetric synthesis of 伪-chiral linear or carbocyclic (纬-alkoxyallyl)boronates via the copper(I)-catalyzed 纬-boryl substitution of allyl acetals. This reaction afforded the products in high yields with excellent E:Z selectivities and enantioselectivities [only (E)-product, 91鈥?8% ee] and also exhibited high functional group compatibility. Subsequent allylation of aldehydes with the 伪-chiral (纬-alkoxyallyl)boronates provided the anti-1,2-diol derivatives in a highly stereospecific manner, and the utility of the 伪-chiral (纬-alkoxyallyl)boronates was further demonstrated by a convergent coupling of a complex polyol derivative using a (纬-alkoxyallyl)boronate and a chiral 伪-oxyaldehyde. The stereoselective modular construction of a complex 3,3-disubstituted cyclopentene containing three consecutive stereocenters including a quaternary chiral carbon was also reported. Useful transformations of the 伪-chiral linear (纬-alkoxyallyl)boronates were also demonstrated.