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钴催化未活化的C(sp) - H键的羰基化反应。

Cobalt catalyzed carbonylation of unactivated C(sp)-H bonds.

作者信息

Barsu Nagaraju, Bolli Shyam Kumar, Sundararaju Basker

机构信息

Fine Chemical Laboratory , Department of Chemistry , Indian Institute of Technology Kanpur , Kanpur , Uttar Pradesh , India . Email:

出版信息

Chem Sci. 2017 Mar 1;8(3):2431-2435. doi: 10.1039/c6sc05026c. Epub 2016 Dec 20.

Abstract

A general efficient regioselective cobalt catalyzed carbonylation of unactivated C(sp)-H bonds of aliphatic amides was demonstrated using atmospheric (1-2 atm) carbon monoxide as a C1 source. This straightforward approach provides access to α-spiral succinimide regioselectively in a good yield. Cobalt catalyzed sp C-H bond carbonylation is reported for the first time including the functionalization of (β)-C-H bonds of α-1°, 2°, 3° carbons and even internal (β)-C-H bonds. Our initial mechanistic investigation reveals that the C-H activation step is irreversible and will possibly be the rate determining step.

摘要

利用常压(1 - 2个大气压)一氧化碳作为C1源,展示了一种通用、高效、区域选择性的钴催化脂肪族酰胺未活化C(sp)-H键的羰基化反应。这种直接的方法能够以良好的产率区域选择性地合成α-螺旋琥珀酰亚胺。首次报道了钴催化的sp C-H键羰基化反应,包括α-1°、2°、3°碳的(β)-C-H键甚至内部(β)-C-H键的官能团化。我们初步的机理研究表明,C-H活化步骤是不可逆的,并且可能是速率决定步骤。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e91c/5369400/8df221c78ea0/c6sc05026c-s1.jpg

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