Gao Shang, Chen Ming
Department of Chemistry and Biochemistry , Auburn University , Auburn , AL 36849 , USA . Email:
Chem Sci. 2019 Jun 28;10(32):7554-7560. doi: 10.1039/c9sc02905b. eCollection 2019 Aug 28.
Cu-catalyzed stereoselective synthesis of ()-δ-silyl--homoallylic alcohols from 1,3-dienylsilane was developed. Mechanistic studies revealed that the borocupration of dienylsilane proceeded through a 1,2-addition pathway to give an allylcopper intermediate with Cu distal to the silyl group. However, the subsequent aldehyde allylation proceeded Curtin-Hammett control to give ()-δ-silyl--homoallylic alcohols with high diastereoselectivities. This method was applied to the synthesis of the C fragment of a polyketide natural product, mycinolide IV.
开发了一种通过铜催化从1,3 - 二烯基硅烷立体选择性合成()-δ-甲硅烷基-γ-高烯丙醇的方法。机理研究表明，二烯基硅烷的硼铜化反应通过1,2 - 加成途径进行，生成一个甲硅烷基远端带有铜的烯丙基铜中间体。然而，随后的醛烯丙基化反应通过柯廷-哈米特控制，以高非对映选择性生成()-δ-甲硅烷基-γ-高烯丙醇。该方法应用于聚酮天然产物麦奇内酯IV的C片段的合成。
