Iridium-catalyzed selective 1,2-hydrosilylation of N-heterocycles

Chemical Science
Jinseong JeongSukbok Chang

Abstract

A silylene-bridged Ir dimer in situ generated from [Ir(coe)2Cl]2 and Et2SiH2 was found to catalyze the hydrosilylation of N-heteroaromatics to furnish dearomatized azacyclic products with high activity (up to 1000 TONs), excellent selectivity, and good functional group tolerance. The substrate scope was highly broad, including (iso)quinolines, substituted pyridines, pyrimidines, pyrazines, deazapurines, triazines, and benzimidazoles. Mechanistic studies such as a kinetic profile, rate-order assessment, and investigation of the electronic substituent effects on the initial rates were performed to access the detailed pathways. One pathway is proposed to involve an intramolecular insertion of the C[double bond, length as m-dash]N moiety of the substrates into the Ir-H bond of a resting species to form an Ir-amido silyl intermediate, followed by reductive elimination. The synthetic utility was proven by successful application to cinchona alkaloids, and facile post-synthetic transformations of the 1,2-dihydroquinoline products.

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Citations

Feb 22, 2018·Chemistry : a European Journal·Heng LiuMoris S Eisen
Feb 7, 2017·Angewandte Chemie·Sehoon Park, Sukbok Chang
May 1, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Liuzhou GaoShuhua Li
Oct 26, 2018·The Journal of Organic Chemistry·Yongjia ShiSenmiao Xu
Dec 2, 2017·Journal of the American Chemical Society·Fanjun ZhangWenguang Wang

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Methods Mentioned

BETA
NMR
column chromatography
X-ray

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