Oxidation-induced nucleophilic substitution at the electron-rich B(12) vertex in [CB11H12]- under catalyst-free conditions

被引：0

作者：

Sun, Wanqi ^{[1
]}

Jin, Yujie ^{[1
,2
]}

Wang, Yongtao ^{[1
,2
]}

Wen, Zeyu ^{[1
]}

Sun, Jizeng ^{[1
]}

Yao, Jia ^{[1
,2
]}

Duttwyler, Simon ^{[1
]}

Li, Haoran ^{[1
,2
,3
]}

机构：

[1] Zhejiang Univ, Dept Chem, 866 Yuhangtang Rd, Hangzhou 310058, Peoples R China

[2] Zhejiang Univ, Ctr Chem Frontier Technol, ZJU NHU United R&D Ctr, 866 Yuhangtang Rd, Hangzhou 310058, Peoples R China

[3] Zhejiang Univ, Coll Chem & Biol Engn, State Key Lab Chem Engn, 866 Yuhangtang Rd, Hangzhou 310058, Peoples R China

来源：

CHEMICAL SCIENCE | 2025年

基金：

中国国家自然科学基金; 国家重点研发计划;

关键词：

B-H FUNCTIONALIZATION; DERIVATIVES; CARBORANES; ANIONS;

D O I：

10.1039/d5sc00234f

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Highly regioselective B(12) substitutions of the monocarborane anion [CB11H12]- has been a challenge. Here, we synthesized a stable B-O-N zwitterionic compound with an impressive yield (isolated yield up to 98%) and excellent regioselectivity at the B(12) position under catalyst-free conditions. The kinetics, substituent effect, and capture experiments are paired with theoretical calculations, showing that the reaction mechanism is oxidation-induced nucleophilic substitution. The hydride anion at the B(12) position is abstracted by an oxoammonium oxidant with lower cleavage energy of 4.2 kcal mol-1 than B(7-11) positions, thereby changing the electronegativity upon the conversion of [CB11H12]- to neutral [CB11H11], in turn giving very high regioselectivity for nucleophilic substitution. This work presents an effective method for synthesizing B(12) oxygen derivatives of the [CB11H12]- anion.

引用

页码：5942 / 5947

页数：6

共 53 条

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