Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore.
Org Lett. 2011 Apr 1;13(7):1622-5. doi: 10.1021/ol200425c. Epub 2011 Mar 7.
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.
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)。