期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 34, 页码 14647-14655出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202006237
关键词
allylic substitution; asymmetric catalysis; noncovalent interactions; palladium; statistical modeling
资金
- National Institutes of Health [GM121383, R35 GM118190]
- Ministry of Science and Technology, Taiwan [106-2917-I-564-056]
- EU [789399]
- NSF [ACI-1548562]
- Marie Curie Actions (MSCA) [789399] Funding Source: Marie Curie Actions (MSCA)
The mode of asymmetric induction in an enantioselective intramolecular allylic substitution reaction catalyzed by a combination of palladium and a chiral phosphoric acid was investigated by a combined experimental and statistical modeling approach. Experiments to probe nonlinear effects, the reactivity of deuterium-labeled substrates, and control experiments revealed that nucleophilic attack to the pi-allylpalladium intermediate is the enantio-determining step, in which the chiral phosphate anion is involved in stereoinduction. Using multivariable linear regression analysis, we determined that multiple noncovalent interactions with the chiral environment of the phosphate anion are integral to enantiocontrol in the transition state. The synthetic protocol to form chiral pyrrolidines was further applied to the asymmetric construction of C-O bonds at fully substituted carbon centers in the synthesis of chiral 2,2-disubstituted benzomorpholines.
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