Transition Metal‐Controlled Direct Regioselective Intermolecular Amidation of C−H Bonds with Azodicarboxylates: Scope, Mechanistic Studies, and Applications. Issue 21 (13th September 2018)

• Record Type: Journal Article
• Authors: Bai, He‐Yuan; Fu, Xin; Pan, Jin‐Long; Ma, Hai‐Qian; Chen, Zhi‐Min; Ding, Tong‐Mei; Zhang, Shu‐Yu
• Is Part Of: Advanced synthesis & catalysis. Volume 360:Issue 21(2018)
• Page Start: 4205
• Page End: 4214
• Publication Date: 2018-09-13
• Subjects: transition metal -- azodicarboxylates -- regioselective -- amidation -- applications; Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.201800623
• Languages: English
• ISSNs: 1615-4150

Abstract

Abstract: 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. Abstract :