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铜（I）催化的环己酮α-碳上不对称全碳双季铵盐中心的合成。

Copper(I)-Catalyzed Synthesis of Unsymmetrical All-Carbon Bis-Quaternary Centers at the Opposing α-Carbons of Cyclohexanones.

机构信息

Department of Chemistry, Louisiana State University, 232 Choppin Hall, Baton Rouge, Louisiana 70803, United States.

出版信息

Org Lett. 2022 Jul 8;24(26):4810-4815. doi: 10.1021/acs.orglett.2c01890. Epub 2022 Jun 29.

DOI:10.1021/acs.orglett.2c01890
PMID:35767696
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9490817/
Abstract

We describe a new synthetic reaction that generates all-carbon bis-quaternary centers at the opposing side of α-carbons in cyclohexanone with four different substituents in a controlled manner. Catalyzed by Cu(MeCN)BF salt, this chemistry is proposed to proceed via an intermediacy of unsymmetrical -allyl oxyallyl cations, which undergo a sequence of regioselective nucleophilic addition with substituted indoles and diastereoselective Claisen rearrangement in a single synthetic operation. The stereochemical outcome of the products features the diastereorelationship between the two aryl groups at the α,α'-positions.

摘要

我们描述了一种新的合成反应，该反应以可控的方式在环己酮的α-碳的相反侧生成具有四个不同取代基的全碳双季铵中心。在 Cu(MeCN)BF 盐的催化下，该反应被认为是通过不对称烯丙氧基烯丙基阳离子中间体进行的，该中间体在单一合成操作中经历了取代吲哚的区域选择性亲核加成和立体选择性 Claisen 重排。产物的立体化学特征是α,α'-位的两个芳基基团之间的非对映关系。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44e2/9490817/b88c8c30d91b/ol2c01890_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44e2/9490817/c353efc76b3a/ol2c01890_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44e2/9490817/be135ef11bb5/ol2c01890_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44e2/9490817/e63c26dcf37d/ol2c01890_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44e2/9490817/b88c8c30d91b/ol2c01890_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44e2/9490817/c353efc76b3a/ol2c01890_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44e2/9490817/be135ef11bb5/ol2c01890_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44e2/9490817/e63c26dcf37d/ol2c01890_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44e2/9490817/b88c8c30d91b/ol2c01890_0004.jpg

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