?
当前位置:澳门黄金赌城 > 小柯机器人 >详情
不对称反阴离子定向光氧化还原催化
作者:小柯机器人 发布时间:2023/1/28 8:37:06

德国马普煤炭研究所Benjamin List团队报道了不对称反阴离子定向光氧化还原催化。相关研究成果于2023年1月19日发表在《科学》。

光氧化还原催化能够实现独特且广泛适用的化学反应,但控制其选择性已被证明是困难的。对映体选择性的追求是一个特别艰巨的挑战,可以说是由于活化的自由基(离子)中间体的高能量,而以前的方法总是需要将光还原催化循环与用于不对称诱导的额外活化模式配对。通过自由基离子进行光还原反应的一个潜在解决方案是与对映纯反离子的催化配对。然而,尽管已经描述了这种方法的尝试,但尚未实现高选择性。

该文中,研究人员报告了基于自由基阳离子的不对称光氧化催化的潜在通用解决方案。研究人员描述了有机盐,其特征是限制的IDPi反离子催化苯乙烯的高度对映选择性[2+2]-交叉环加成。

附:英文原文

Title: Asymmetric counteranion-directed photoredox catalysis

Author: Sayantani Das, Chendan Zhu, Derya Demirbas, Eckhard Bill, Chandra Kanta De, Benjamin List

Issue&Volume: 2023-01-19

Abstract: Photoredox catalysis enables unique and broadly applicable chemical reactions but controlling their selectivity has proven to be difficult. The pursuit of enantioselectivity is a particularly daunting challenge, arguably due to the high energy of the activated radical (ion) intermediates, and previous approaches have invariably required pairing of the photoredox catalytic cycle with an additional activation mode for asymmetric induction. A potential solution for photoredox reactions proceeding via radical ions would be catalytic pairing with enantiopure counterions. However, while attempts toward this approach have been described, high selectivity has not yet been accomplished. Here we report a potentially general solution to radical cation-based asymmetric photoredox catalysis. We describe organic salts, featuring confined IDPi counteranions that catalyze highly enantioselective [2+2]-cross cycloadditions of styrenes.

DOI: ade8190

Source: https://www.science.org/doi/10.1126/science.ade8190

 

期刊信息

Science:《科学》,创刊于1880年。隶属于美国科学促进会,最新IF:63.714
官方网址:https://www.sciencemag.org/
投稿链接:https://cts.sciencemag.org/scc/#/login

?