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铑-氮杂环卡宾催化的末端炔烃的偕位特异性O-选择性氢吡啶化反应

Rhodium-NHC-Catalyzed gem-Specific O-Selective Hydropyridonation of Terminal Alkynes.

作者信息

Galiana-Cameo María, Romeo Raúl, Urriolabeitia Asier, Passarelli Vincenzo, Pérez-Torrente Jesús J, Polo Victor, Castarlenas Ricardo

机构信息

Departamento de Química Inorgánica-Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Universidad de Zaragoza-CSIC, C/Pedro Cerbuna 12, CP, 50009, Zaragoza, Spain.

Departamento de Química Física, Universidad de Zaragoza, C/Pedro Cerbuna 12, CP, 50009, Zaragoza, Spain.

出版信息

Angew Chem Int Ed Engl. 2022 May 9;61(20):e202117006. doi: 10.1002/anie.202117006. Epub 2022 Mar 19.

DOI:10.1002/anie.202117006
PMID:35262264
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9311084/
Abstract

The dinuclear complex [Rh(μ-Cl)(η -coe)(IPr)] is an efficient catalyst for the O-selective Markovnikov-type addition of 2-pyridones to terminal alkynes. DFT calculations support a hydride-free pathway entailing intramolecular oxidative protonation of a π-alkyne by a κ N-hydroxypyridine ligand. Subsequent O-nucleophilic attack on a metallacyclopropene species affords an O-alkenyl-2-oxypyridine chelate rhodium intermediate as the catalyst resting state. The release of the alkenyl ether is calculated as the rate-determining step.

摘要

双核配合物[Rh(μ-Cl)(η -coe)(IPr)]是一种高效催化剂，可用于2-吡啶酮与末端炔烃的O-选择性马氏加成反应。密度泛函理论计算支持一种无氢化物途径，该途径涉及κN-羟基吡啶配体对π-炔烃的分子内氧化质子化。随后，O-亲核进攻金属环丙烯物种，得到O-烯基-2-氧代吡啶螯合铑中间体作为催化剂的静止状态。烯基醚的释放被计算为速率决定步骤。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6ef7/9311084/7bccbe4b6579/ANIE-61-0-g001.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6ef7/9311084/68558d5ed5bc/ANIE-61-0-g006.jpg
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