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铜催化的氧气氛围下的苄位 C-H 氧化反应,通过 N-H 亚胺作为分子内导向基团。

Copper-catalyzed benzylic C-H oxygenation under an oxygen atmosphere via N-H imines as an intramolecular directing group.

机构信息

Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore.

出版信息

Org Lett. 2011 Apr 1;13(7):1622-5. doi: 10.1021/ol200425c. Epub 2011 Mar 7.

Abstract

Copper-catalyzed benzylic C-H oxygenation under an oxygen atmosphere was developed starting from carbonitriles and Grignard reagents via N-H imine intermediates. The present process is characterized by the following two-step sequence in a one-pot manner: (1) addition of Grignard reagents to carbonitriles to form N-H imines and (2) benzylic C-H oxygenation (C═O bond formation) triggered by 1,5-hydrogen atom transfer with transient iminyl copper species.

摘要

在氧气氛围下,铜催化的苄基 C-H 氧化反应从腈和格氏试剂出发,通过 N-H 亚胺中间体发展而来。该过程的特点是通过两步一锅法进行:(1)格氏试剂加成到腈上形成 N-H 亚胺,(2)瞬态亚胺基铜物种引发的 1,5-氢原子转移的苄基 C-H 氧化(C═O 键形成)。

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