通过由消失的三甲基硅基引导的环氧化物开环级联反应合成梯形聚醚。
Ladder polyether synthesis via epoxide-opening cascades directed by a disappearing trimethylsilyl group.
机构信息
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
出版信息
J Org Chem. 2010 Apr 16;75(8):2681-701. doi: 10.1021/jo1002455.
Abstract
Epoxide-opening cascades offer the potential to construct complex polyether natural products expeditiously and in a manner that emulates the biogenesis proposed for these compounds. Herein we provide a full account of our development of a strategy that addresses several important challenges of such cascades. The centerpiece of the method is a trimethylsilyl (SiMe(3)) group that serves several purposes and leaves no trace of itself by the time the cascade has come to an end. The main function of the SiMe(3) group is to dictate the regioselectivity of epoxide opening. This strategy is the only general method of effecting endo-selective cascades under basic conditions.
摘要
环氧化合物开环级联反应为迅速构建复杂的聚醚天然产物提供了可能，并且这种方法模拟了这些化合物的生物合成途径。在此，我们提供了一种策略的完整描述，该策略解决了此类级联反应的几个重要挑战。该方法的核心是三甲硅基（SiMe(3)）基团，它具有多种功能，并且在级联反应结束时不会留下任何痕迹。SiMe(3)基团的主要功能是决定环氧化物开环的区域选择性。这种策略是在碱性条件下实现内选择性级联反应的唯一通用方法。
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