当前位置: X-MOL 学术Science › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Carbonyl catalysis enables a biomimetic asymmetric Mannich reaction
Science ( IF 56.9 ) Pub Date : 2018-06-28 , DOI: 10.1126/science.aat4210
Jianfeng Chen 1, 2 , Xing Gong 1 , Jianyu Li 1 , Yingkun Li 1 , Jiguo Ma 1 , Chengkang Hou 1 , Guoqing Zhao 1 , Weicheng Yuan 2 , Baoguo Zhao 1
Affiliation  

Inspiration from a vitamin Organic synthesis of molecules with defined stereochemistry requires a chiral center, which in turn may involve a chiral catalyst. Chen et al. developed an organic catalyst, modeled on vitamin B6, which contains an electron-withdrawing pyridine ring adjacent to an aldehyde group. This catalyst works like the vitamin by reacting with an amine, a derivative of the amino acid glycine, to create an activated species. An appendage on the catalyst coordinates the subsequent reactions, allowing for stereoselective formation of a product with two adjacent amines. Science, this issue p. 1438 A vitamin-inspired organic catalyst brings together an amine and an imine to yield α,β-diamino acid esters. 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 N-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.

中文翻译:

羰基催化使仿生不对称曼尼希反应成为可能

维生素的灵感 具有明确立体化学的分子的有机合成需要手性中心,而手性中心又可能涉及手性催化剂。陈等人。开发了一种以维生素 B6 为模型的有机催化剂,其中包含一个与醛基相邻的吸电子吡啶环。这种催化剂的作用类似于维生素,它与胺(氨基酸甘氨酸的衍生物)反应以产生活化的物质。催化剂上的一个附属物协调随后的反应,允许立体选择性地形成具有两个相邻胺的产物。科学,这个问题 p。1438 受维生素启发的有机催化剂将胺和亚胺结合在一起,生成 α,β-二氨基酸酯。手性胺广泛用作不对称合成中的催化剂,以活化羰基进行α-官能化。羰基催化通过使用羰基激活伯胺来逆转该策略。受生物羰基催化(以吡哆醛依赖性酶的反应为例)的启发,我们开发了一种 N-季铵化吡哆醛催化剂,用于甘氨酸酯与芳基 N-二苯基膦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,可能是通过底物的类酶协同双功能活化来实现的。我们的工作证明了吡哆醛部分在不对称催化中的催化效用。我们开发了一种 N-季铵化吡哆醛催化剂,用于甘氨酸酯与芳基 N-二苯基膦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,可能是通过底物的类酶协同双功能活化来实现的。我们的工作证明了吡哆醛部分在不对称催化中的催化效用。我们开发了一种 N-季铵化吡哆醛催化剂,用于甘氨酸酯与芳基 N-二苯基膦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,可能是通过底物的类酶协同双功能活化来实现的。我们的工作证明了吡哆醛部分在不对称催化中的催化效用。
更新日期:2018-06-28
down
wechat
bug