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TBHP‐Initiated Transamidation of Secondary Amides via C−N Bond Activation: A Metal‐Free Approach
Author(s) -
Mishra Ankush,
Chauhan Swati,
Verma Pratibha,
Singh Sundaram,
Srivastava Vandana
Publication year - 2019
Publication title -
asian journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.846
H-Index - 44
eISSN - 2193-5815
pISSN - 2193-5807
DOI - 10.1002/ajoc.201900128
Subject(s) - chemistry , amide , functional group , steric effects , primary (astronomy) , combinatorial chemistry , substrate (aquarium) , environmentally friendly , catalysis , radical initiator , reaction conditions , radical , organic chemistry , polymer chemistry , ecology , physics , oceanography , astronomy , polymerization , biology , geology , polymer
In the present study, a facile, efficient, and environmentally benign approach for secondary amide transamidation by using tert ‐butyl hydroperoxide (TBHP) as a radical initiator has been developed. The method involves a two‐step approach in which the first step is the C−N bond activation via N‐functionalization with Boc to weaken the amide C−N bond by making amide non‐planar and electronically destabilized. In the second step, an N‐Boc‐activated secondary amides undergoes transamidation with the various primary, secondary, aliphatic, aromatic, as well as the sterically hindered amines, using TBHP as a radical initiator to give the products in good to excellent yields. TBHP is easily available, inexpensive, and an environmentally friendly radical initiator. A broad substrate scope with extensive functional group tolerance, metal and catalyst‐free approach, and operational simplicity are the important characteristics of the present protocol.