发布时间：

2025-11

影响因子：

11.7

DOI码：

10.1126/sciadv.adg1237

论文名称：

Nature-inspired catalytic asymmetric rearrangement of cyclopropylcarbinyl cation

发表刊物：

SCIENCE ADVANCES

摘要：

In nature, cyclopropylcarbinyl cation is often involved in cationic cascade reactions catalyzed by natural enzymes to produce a great number of structurally diverse natural substances. However, mimicking this natural process with artificial organic catalysts remains a daunting challenge in synthetic chemistry. We report a small molecule-catalyzed asymmetric rearrangement of cyclopropylcarbinyl cations, leading to a series of chiral homoallylic sulfide products with good to excellent yields and enantioselectivities (up to 99% enantiomeric excess). In the presence of a chiral SPINOL-derived N-triflyl phosphoramide catalyst, the dehydra-tion of prochiral cyclopropylcarbinols occurs rapidly to generate symmetrical cyclopropylcarbinyl cations, which are subsequently trapped by thione-containing nucleophiles. A subgram-scale experiment and multiple down-stream transformations of the sulfide products are further pursued to demonstrate the synthetic utility. Notably, a few heteroaromatic sulfone derivatives could serve as "covalent warhead" in the enzymatic inhibition of severe acute respiratory syndrome coronavirus 2 main protease.

第一作者：

liqinghua,zhangguishan

论文类型：

期刊论文

通讯作者：

王雨卉,leealbertwm,gaodingding,田平

卷号：

9

期号：

19

ISSN号：

2375-2548

是否译文：

否

发表时间：

2023-05

他引次数：

10