Catalytic, Metal-Free Amide Synthesis from Aldehydes and Imines Enabled by a Dual-Catalyzed Umpolung Strategy under Redox-Neutral Conditions

被引:83
作者
Liu, Ming-Shang [1 ,2 ]
Shu, Wei [1 ,2 ]
机构
[1] Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Guangdong, Peoples R China
[2] Southern Univ Sci & Technol, Dept Chem, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Guangdong, Peoples R China
关键词
amide synthesis; C-N bond forming; NHC catalysis; visible-light catalysis; dual catalysis; umpolung; atom economy; radical-radical coupling; LIGHT PHOTOREDOX CATALYSIS; N-HETEROCYCLIC CARBENE; CARBOXYLIC-ACIDS; THIAMINE ACTION; RADICALS; AMIDATION; MECHANISM; ALCOHOLS; AMINES; ARYL;
D O I
10.1021/acscatal.0c04070
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The synthesis of amides is a long-term theme in chemistry and related areas. The use of readily available and cost-effective precursors for straightforward amide synthesis with atom economy under mild conditions is attractive yet challenging. Herein, we report the direct synthesis of amides from aldehydes and imines in a 100% atom-economical manner. The redox-neutral C-N bond-forming process was enabled by the dual catalysis of visible light and an N-heterocyclic carbene (NHC) at room temperature. This protocol features the unprecedented umpolung of imines to generate N-centered radicals. Mechanistic investigations reveal this reaction undergoes nontrivial radical-radical coupling between an N-centered radical and a C-centered radical to forge a C-N bond. This operationally simple protocol tolerates a wide range of functional groups, providing rapid access to amides from aromatic or aliphatic aldehydes with imines without producing any byproduct.
引用
收藏
页码:12960 / 12966
页数:7
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