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源自2-葑氧基或2-薄荷氧基芳基乙酸的二铑羧酸盐催化剂：对映选择性C-H插入、芳基加成及氧鎓叶立德的形成/重排

Dirhodium Carboxylate Catalysts from 2-Fenchyloxy or 2-Menthyloxy Arylacetic Acids: Enantioselective C-H Insertion, Aromatic Addition and Oxonium Ylide Formation/Rearrangement.

作者信息

Buckley Aoife M, Crowley Daniel C, Brouder Thomas A, Ford Alan, Rao Khandavilli U B, Lawrence Simon E, Maguire Anita R

机构信息

School of Chemistry Analytical and Biological Chemistry Research Facility University College Cork Cork Ireland.

School of Chemistry and School of Pharmacy Analytical and Biological Chemistry Research Facility Synthesis and Solid State Pharmaceutical Centre University College Cork Cork Ireland.

出版信息

ChemCatChem. 2021 Oct 19;13(20):4318-4324. doi: 10.1002/cctc.202100924. Epub 2021 Aug 23.

DOI:10.1002/cctc.202100924
PMID:34820025
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8597163/
Abstract

A new class of dirhodium carboxylate catalysts have been designed and synthesized from 2-fenchyloxy or 2-menthyloxy arylacetic acids which display excellent enantioselectivity across a range of transformations of α-diazocarbonyl compounds. The catalysts were successfully applied to enantioselective C-H insertion reactions of aryldiazoacetates and α-diazo-β-oxosulfones affording the respective products in up to 93 % ee with excellent trans diastereoselectivity in most cases. Furthermore, efficient desymmetrization in an intramolecular C-H insertion was achieved. In addition, these catalysts prove highly enantioselective for intramolecular aromatic addition with up to 88 % ee, and oxonium ylide formation and rearrangement with up to 74 % ee.

摘要

一类新型的二铑羧酸盐催化剂已由2-葑氧基或2-薄荷氧基芳基乙酸设计合成，这些催化剂在一系列α-重氮羰基化合物的转化反应中表现出优异的对映选择性。该催化剂已成功应用于芳基重氮乙酸酯和α-重氮-β-氧代砜的对映选择性C-H插入反应，在大多数情况下，相应产物的对映体过量率高达93%，具有优异的反式非对映选择性。此外，还实现了分子内C-H插入反应中的高效去对称化。此外，这些催化剂在分子内芳香族加成反应中表现出高达88%的对映体过量率，在氧鎓叶立德的形成和重排反应中表现出高达74%的对映体过量率，显示出高对映选择性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/08d8/8597163/af3e5a978256/CCTC-13-4318-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/08d8/8597163/54b7755ec68d/CCTC-13-4318-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/08d8/8597163/38b1aa93f104/CCTC-13-4318-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/08d8/8597163/fe8a67202915/CCTC-13-4318-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/08d8/8597163/7ee49156cabd/CCTC-13-4318-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/08d8/8597163/44410963025e/CCTC-13-4318-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/08d8/8597163/64facf1e5dad/CCTC-13-4318-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/08d8/8597163/af3e5a978256/CCTC-13-4318-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/08d8/8597163/54b7755ec68d/CCTC-13-4318-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/08d8/8597163/38b1aa93f104/CCTC-13-4318-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/08d8/8597163/fe8a67202915/CCTC-13-4318-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/08d8/8597163/7ee49156cabd/CCTC-13-4318-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/08d8/8597163/44410963025e/CCTC-13-4318-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/08d8/8597163/64facf1e5dad/CCTC-13-4318-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/08d8/8597163/af3e5a978256/CCTC-13-4318-g004.jpg

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