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作为瞬态羟烷基官能化 N-杂环卡宾的手性恶唑烷：一种获得用于不对称催化的空气稳定铜和金配合物的有效途径。

Chiral oxazolidines acting as transient hydroxyalkyl-functionalized N-heterocyclic carbenes: an efficient route to air stable copper and gold complexes for asymmetric catalysis.

作者信息

Pichon-Barré Delphine, Zhang Ziyun, Cador Aël, Vives Thomas, Roisnel Thierry, Baslé Olivier, Jarrige Lucie, Cavallo Luigi, Falivene Laura, Mauduit Marc

机构信息

Univ Rennes, Ecole Nationale Supérieure de Chimie de Rennes, CNRS, ISCR UMR 6226 F-35000 Rennes France

King Abdullah University of Science and Technology (KAUST), Chemical and Life Sciences and Engineering, Kaust Catalysis Center Thuwal 23955-6900 Saudi Arabia

出版信息

Chem Sci. 2022 Jul 11;13(30):8773-8780. doi: 10.1039/d2sc02908a. eCollection 2022 Aug 4.

DOI:10.1039/d2sc02908a
PMID:35975143
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9350591/
Abstract

Optically pure oxazolidines were synthesized in nearly quantitative yields from chiral hydroxyalkyl-functionalized imidazolinium salts. Acting as transient chiral diamino N-heterocyclic carbenes (NHCs), these oxazolidines allowed the efficient formation of well-defined copper(i) and gold(i) hydroxyalkyl-NHC complexes, which could be isolated, for the first time, as air stable complexes after silica gel chromatography. Interestingly, X-ray analysis of gold complexes revealed that the hydroxyl-function is not chelated to the metal. Computational studies suggested that both cyclisation to produce oxazolidine and O-H bond elimination to form the transient carbene (prior to coordination) occur through a concerted mechanism. The novel chiral copper-catalysts, as well as oxazolidines alone (copper free), demonstrated excellent performances in asymmetric conjugate addition and allylic alkylation with high regio- and enantio-selectivities (up to 99% ee).

摘要

从手性羟烷基官能化咪唑鎓盐出发，以几乎定量的产率合成了光学纯的恶唑烷。这些恶唑烷作为瞬态手性二氨基氮杂环卡宾（NHCs），能够高效地形成结构明确的铜（I）和金（I）羟烷基-NHC配合物，经硅胶柱色谱分离后，首次可作为空气稳定的配合物分离出来。有趣的是，金配合物的X射线分析表明，羟基官能团未与金属螯合。计算研究表明，生成恶唑烷的环化反应以及形成瞬态卡宾（配位之前）的O-H键消除反应均通过协同机理发生。新型手性铜催化剂以及单独的恶唑烷（无铜）在不对称共轭加成和烯丙基烷基化反应中表现出优异的性能，具有高区域选择性和对映选择性（高达99% ee）。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/a24ef376d0ea/d2sc02908a-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/057bd0d955f0/d2sc02908a-f1.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/91001141c91e/d2sc02908a-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/348aec25deca/d2sc02908a-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/951c1e311223/d2sc02908a-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/36fd40ed870d/d2sc02908a-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/c5cb19a202f2/d2sc02908a-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/8d6c154f8052/d2sc02908a-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/0c659b7d7c62/d2sc02908a-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/a24ef376d0ea/d2sc02908a-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/057bd0d955f0/d2sc02908a-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/1dafb0a63930/d2sc02908a-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/91001141c91e/d2sc02908a-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/348aec25deca/d2sc02908a-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/951c1e311223/d2sc02908a-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/36fd40ed870d/d2sc02908a-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/c5cb19a202f2/d2sc02908a-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/8d6c154f8052/d2sc02908a-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/0c659b7d7c62/d2sc02908a-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e696/9350591/a24ef376d0ea/d2sc02908a-s5.jpg

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