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通过镍催化不对称乌尔曼偶联反应合成轴向手性 2,2'-双膦酰基联苯:无需光学拆分即可获得手性配体的通用方法。

Synthesis of Axially Chiral 2,2'-Bisphosphobiarenes via a Nickel-Catalyzed Asymmetric Ullmann Coupling: General Access to Privileged Chiral Ligands without Optical Resolution.

机构信息

Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States.

出版信息

J Am Chem Soc. 2021 Jan 27;143(3):1328-1333. doi: 10.1021/jacs.0c12843. Epub 2021 Jan 13.

DOI:10.1021/jacs.0c12843
PMID:33439640
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8173523/
Abstract

We report an asymmetric homocoupling of (iodo)arylphosphine oxides and -(iodo)arylphosphonates resulting in highly enantioenriched axially chiral bisphosphine oxides and bisphosphonates. These products are readily converted to enantioenriched biaryl bisphosphines without need for chiral auxiliaries or optical resolution. This provides a practical route for the development of previously uninvestigated atroposelective biaryl bisphosphine ligands. The conditions have also proven effective for asymmetric dimerization of other, non-phosphorus-containing aryl halides.

摘要

我们报告了(碘)芳基膦氧化物和-(碘)芳基膦酸酯的不对称同偶联反应,得到了高度对映富集的轴手性双膦氧化物和双膦酸酯。这些产物可以很容易地转化为对映富集的联芳基双膦配体,而无需使用手性助剂或光学拆分。这为开发以前未研究过的轴手性联芳基双膦配体提供了一种实用的途径。这些条件也被证明对其他非磷含芳基卤化物的不对称二聚反应有效。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fed6/8173523/63e448497fd5/nihms-1707040-f0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fed6/8173523/329902525883/nihms-1707040-f0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fed6/8173523/63e448497fd5/nihms-1707040-f0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fed6/8173523/329902525883/nihms-1707040-f0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fed6/8173523/63e448497fd5/nihms-1707040-f0003.jpg

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