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铜催化的 B-取代烯丙基亲核试剂与羰基的加成反应，实现了立体选择性、对映选择性和二级醇及季碳立体中心的形成。

Diastereo-, Enantio-, and Selective Formation of Secondary Alcohol and Quaternary Carbon Stereocenters by Cu-Catalyzed Additions of B-Substituted Allyl Nucleophiles to Carbonyls.

机构信息

Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, United States.

出版信息

Org Lett. 2020 Dec 4;22(23):9269-9275. doi: 10.1021/acs.orglett.0c03495. Epub 2020 Nov 18.

DOI:10.1021/acs.orglett.0c03495
PMID:33206543
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7797407/
Abstract

A general method for the synthesis of secondary homoallylic alcohols containing α-quaternary carbon stereogenic centers in high diastereo- and enantioselectivity (up to >20:1 dr and >99:1 er) is disclosed. Transformations employ readily accessible aldehydes, allylic diboronates, and a chiral copper catalyst and proceed by γ-addition of in situ generated enantioenriched boron-stabilized allylic copper nucleophiles. The catalytic protocol is general for a wide variety of aldehydes as well as a variety of 1,1-allylic diboronic esters. Hammett studies disclose that diastereoselectivity of the reaction is correlated to the electronic nature of the aldehyde, with dr increasing as aldehydes become more electron poor.

摘要

本研究揭示了一种高效合成含α-季碳手性中心的二级偕丙醇的通用方法，具有优异的非对映选择性（高达>20:1 dr 和 >99:1 er）和对映选择性。该转化采用易得的醛、烯丙基二硼酸酯和手性铜催化剂，通过原位生成的手性硼稳定的烯丙基铜亲核试剂进行γ加成反应。该催化体系对各种醛以及各种 1,1-烯丙基二硼酸酯均具有普适性。哈米特研究表明，反应的非对映选择性与醛的电子性质有关，随着醛的电子密度降低，dr 值增加。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/007a/7797407/b6103856dd20/nihms-1658517-f0009.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/007a/7797407/b8ca26357d83/nihms-1658517-f0006.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/007a/7797407/b6103856dd20/nihms-1658517-f0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/007a/7797407/210bccde301b/nihms-1658517-f0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/007a/7797407/6cf5d3eac159/nihms-1658517-f0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/007a/7797407/b8ca26357d83/nihms-1658517-f0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/007a/7797407/a3a01bd344de/nihms-1658517-f0007.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/007a/7797407/b6103856dd20/nihms-1658517-f0009.jpg

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