解耦(概率)
概括性
路径(计算)
计算机科学
工程类
经济
控制工程
管理
程序设计语言
作者
Li Fan,Jun-Bin Tang,Lilei Wang,Ji-Ren Liu,Zhongliang Li,Yu-Shuai Zhang,Dai-Lei Yuan,Qin Li,Liang Cheng,Qiang‐Shuai Gu,Xin Hong,Zhe Dong,Xin‐Yuan Liu
标识
DOI:10.26434/chemrxiv-2024-3n41t
摘要
Reaction generality is essential for evaluating the value and impact of a synthetic method. However, asymmetric catalysis, particularly that involving highly reactive species such as radicals, typically prioritizes enantioselectivity at the expense of generality. Selectivity and reactivity often conflict because the bond-forming step is usually also stereodetermining. If these two steps were separated, the reaction selectivity and generality issues could then be addressed independently. Herein we report a catalytic asymmetric radical coupling with great generality by merging the copper-catalyzed enantioselective S(IV) center formation and copper-mediated enantiospecific SH2 radical coupling. This decoupling strategy has enabled the successful coupling of over 30 different carbon-, nitrogen-, and oxygen-based radicals having a broad range of reactivity with N-acyl sulfenamides, leading to diverse S-chiral compounds with exceptional enantioselectivity. Thus, it offers a holistic approach to accessing a rich portfolio of S(IV) and S(VI) chiral centers, which is anticipated to have a transformative impact on the synthesis of S-chiral compounds and benefit medicinal chemistry and other related fields. Furthermore, this decoupling strategy via SH2 processes has promising potential to enable a comprehensive single-electron methodology for forging other chiral centers with heteroatoms such as phosphorous(III) and silicon(IV), and eventually also carbon atoms.
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