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通过缩合自由基加成诱导远程官能团迁移和 Horner-Wadsworth-Emmons(HWE)烯烃化反应构建多取代环己烯。

Multisubstituted Cyclohexene Construction through Telescoped Radical-Addition Induced Remote Functional Group Migration and Horner-Wadsworth-Emmons (HWE) Olefination.

机构信息

Technical Institute of Fluorochemistry (TIF), Institute of Advanced Synthesis (IAS), School of Chemistry and Molecular Engineering, Nanjing Tech University, 30 South Puzhu Road, Nanjing, 211816, China.

出版信息

Org Lett. 2021 Dec 17;23(24):9611-9615. doi: 10.1021/acs.orglett.1c03821. Epub 2021 Dec 6.

Abstract

An efficient telescoped method for the rapid assembly of multisubstituted cyclohexenes is presented herein. The whole process nicely merges photoredox-promoted alkene difunctionalization via remote functional group migration with concomitant intramolecular Horner-Wadsworth-Emmons (HWE) olefination. The characteristic feature of this protocol resides in the fact that the follow-up requiring ketone functionality for ring-closing olefination is in situ unveiled from the otherwise inert tertiary alcohol by the preceding alkene difunctionalization.

摘要

本文提出了一种高效的缩合方法,可快速构建多取代环己烯。整个过程巧妙地结合了光氧化还原促进的远程官能团迁移的烯烃双官能化反应,以及伴随的分子内 Horner-Wadsworth-Emmons(HWE)烯烃化反应。该方法的特点在于,后续环化烯烃化所需的酮官能团可以通过前面的烯烃双官能化反应,从原本惰性的叔醇中就地生成。

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