The Education Ministry Key Lab of Resource Chemistry and Shanghai Key Laboratory of Rare Earth Functional Materials, Shanghai Normal University, Shanghai 200234, China.
Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China.
Science. 2018 Jun 29;360(6396):1438-1442. doi: 10.1126/science.aat4210.
Chiral amines are widely used as catalysts in asymmetric synthesis to activate carbonyl groups for α-functionalization. Carbonyl catalysis reverses that strategy by using a carbonyl group to activate a primary amine. Inspired by biological carbonyl catalysis, which is exemplified by reactions of pyridoxal-dependent enzymes, we developed an N-quaternized pyridoxal catalyst for the asymmetric Mannich reaction of glycinate with aryl -diphenylphosphinyl imines. The catalyst exhibits high activity and stereoselectivity, likely enabled by enzyme-like cooperative bifunctional activation of the substrates. Our work demonstrates the catalytic utility of the pyridoxal moiety in asymmetric catalysis.
手性胺广泛用作不对称合成中的催化剂，用于激活羰基以进行 α-官能化。羰基催化通过使用羰基基团来激活伯胺来逆转该策略。受生物羰基催化的启发，生物羰基催化的例子是依赖吡哆醛的酶的反应，我们开发了一种 N-季铵化的吡哆醛催化剂，用于甘氨酸与芳基-二苯膦基亚胺的不对称曼尼希反应。该催化剂表现出高活性和立体选择性，可能是通过类似于酶的协同双功能激活底物来实现的。我们的工作证明了吡哆醛部分在手性催化中的催化实用性。
