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Transition Metal‐Controlled Direct Regioselective Intermolecular Amidation of C−H Bonds with Azodicarboxylates: Scope, Mechanistic Studies, and Applications
Author(s) -
Bai HeYuan,
Fu Xin,
Pan JinLong,
Ma HaiQian,
Chen ZhiMin,
Ding TongMei,
Zhang ShuYu
Publication year - 2018
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201800623
Subject(s) - chemistry , regioselectivity , palladium , catalysis , amide , combinatorial chemistry , methylene , intermolecular force , quinoline , transition metal , stereochemistry , molecule , organic chemistry
A simple and efficient transition metal‐catalyzed C−H amidation with azodicarboxylates has been developed. Under silver catalysis, the amide substrates undergo regioselective C−H amidation at C5‐position of the quinoline. Conversely, with palladium as the catalyst, the reaction gave β‐C( sp 3 )−H amidation products via the activation of methylene C( sp 3 )−H bonds. Mechanistic studies suggested that the single‐electron‐transfer and organometallic mechanism pathways gave rise to these surprising and distinct outcomes. Based on the mechanistic analysis, we designed a palladium‐catalyzed/silver‐promoted direct intermolecular β‐C( sp 3 )−H amidation to activate the methylene C( sp 3 )−H bonds of 5‐chloro‐8‐aminoquinoline (CQ)‐protected aliphatic amides with azodicarboxylates. Both catalytic protocols provide alternative, convenient, and simple strategies for efficiently accessing structurally unique C−N bond‐containing compounds in a regioselective manner.