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Agostic 铱钳形配合物作为一种高效、选择性的 1-烯烃异构化为反式-2-烯烃的催化剂。

An Agostic Iridium Pincer Complex as a Highly Efficient and Selective Catalyst for Monoisomerization of 1-Alkenes to trans-2-Alkenes.

机构信息

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, 345 Lingling Rd, Shanghai, 200032, China.

出版信息

Angew Chem Int Ed Engl. 2017 Feb 1;56(6):1614-1618. doi: 10.1002/anie.201611007. Epub 2017 Jan 2.

DOI:10.1002/anie.201611007
PMID:28042692
Abstract

A unique Ir complex ( NC P)Ir with the pyridine-phosphine pincer as the sole ligand, featuring a dual agostic interaction between the Ir and two σ C-H bonds from a tBu substituent, has been prepared. This complex exhibits exceptionally high activity and excellent regio- and stereoselectivity for monoisomerization of 1-alkenes to trans-2-alkenes with wide functional-group tolerance. Reactions can be performed in neat reactant on a more than 100 gram scale using 0.005 mol % catalyst loadings with turnover numbers up to 19000.

摘要

已制备出一种独特的 Ir 配合物(NC P)Ir,其唯一配体为吡啶-膦钳形配体,Ir 与叔丁基上的两个 σ C-H 键之间存在双重超共轭相互作用。该配合物对 1-烯烃异构化为反式 2-烯烃具有极高的活性和优异的区域和立体选择性,并且对官能团具有广泛的耐受性。反应可以在反应物中进行,在 100 克以上的规模下,使用 0.005 mol%的催化剂负载量,反应数高达 19000。

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