金属转移
化学
磺酰
催化作用
氧化还原
芳基
反应性(心理学)
催化循环
药物化学
组合化学
立体化学
有机化学
烷基
医学
替代医学
病理
作者
Zhaoyin Zhang,Ma Qin,Xing Yang,Shuqi Zhang,Kai Guo,Lili Zhao
摘要
Abstract Sulfonyl fluorides hold significant importance as highly valued intermediates in chemical biology due to their optimal balance of biocompatibility with both aqueous stability and protein reactivity. The Cornella group introduced a one‐pot strategy for synthesizing aryl sulfonyl fluorides via Bi(III) redox‐neutral catalysis, which facilitates the transmetallation and direct insertion of SO 2 into the BiC(sp 2 ) bond giving the aryl sulfonyl fluorides. We report herein a comprehensive computational investigation of the redox‐neutral Bi(III) catalytic mechanism, disclose the critical role of the Bi(III) catalyst and base (i.e., K 3 PO 4 ), and uncover the origin of SO 2 insertion into the Bi(III)C(sp 2 ) bond. The entire catalysis can be characterized via three stages: (i) transmetallation generating the Bi(III)‐phenyl intermediate IM3 facilitated by K 3 PO 4 . (ii) SO 2 insertion into IM3 leading to the formation of Bi(III)‐OSOAr intermediate IM5 . (iii) IM5 undergoes S(IV)‐oxidation yielding the aryl sulfonyl fluoride product 4 and liberating the Bi(III) catalyst for the next catalytic cycle. Each stage is kinetically and thermodynamically feasible. Moreover, we explored other some small molecules (NO 2 , CO 2 , H 2 O, N 2 O, etc.) insertion reactions mediated by the Bi(III)‐complex, and found that NO 2 insertions could be easily achieved due to the low insertion barriers (i.e., 17.5 kcal/mol). Based on the detailed mechanistic study, we further rationally designed additional Bi(III) and Sb(III) catalysts, and found that some of which exhibit promising potential for experimental realization due to their low barriers (<16.4 kcal/mol). In this regard, our study contributes significantly to enhancing current Bi(III)‐catalytic systems and paving the way for novel Bi(III)‐catalyzed aryl sulfonyl fluoride formation reactions.
科研通智能强力驱动
Strongly Powered by AbleSci AI