期刊
CHEMCATCHEM
卷 11, 期 16, 页码 4064-4071出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cctc.201900543
关键词
organocatalysis; N-sulfonyl-binamprolinamide; asymmetric catalysis; DFT calculations; ketone
资金
- CERCA Programme/Generalitat the Catalunya
- MINECO [CTQ2017-87792-R, CTQ2016-75350-P]
- National Natural Science Foundation of China [21703195]
The organocatalyzed synthesis of the Wieland-Miescher ketone (WMK) via N-sulfonyl-binamprolinamide catalysis was investigated using experimental and computational tools. A mechanistic proposal is presented describing the origin of the high enantioselectivity, which rivals that of aldolases. The computational study reveals that the role of the prolinamide catalyst is to lower the reaction barrier and determine the stereoselectivity of the product achieved, while the role of the carboxylic acid is to facilitate proton transfer steps. The effect of the acid cocatalyst was confirmed by experiments. The role of the structure of the BINAM backbone and the effect of the sulfonamide group are uncovered experimentally and computationally. Calculations show that a rigid highly defined catalytic pocket due to covalent and steric interactions induces conformational changes in the triketone substrate to maximize interactions.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据