1,1-Hydroboration and a Borane Adduct of Diphenyldiazomethane: A Potential Prelude to FLP-N2 Chemistry

被引：90

作者：

Tang, Connie ^{[1
]}

Liang, Quiming ^{[1
]}

Jupp, Andrew R. ^{[1
]}

Johnstone, Timothy C. ^{[1
]}

Neu, Rebecca C. ^{[1
]}

Song, Datong ^{[1
]}

Grimme, Stefan ^{[2
]}

Stephan, Douglas W. ^{[1
]}

机构：

[1] Univ Toronto, Dept Chem, 80 St George St, Toronto, ON M5S 3H6, Canada

[2] Univ Bonn, Mulliken Ctr Theoret Chem, Inst Phys & Theoret Chem, D-53115 Bonn, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2017年 / 56卷 / 52期

基金：

加拿大自然科学与工程研究理事会;

关键词：

adducts; boranes; diphenyldiazomethane; hydroboration; nitrogen; FRUSTRATED LEWIS PAIRS; NITROUS-OXIDE; ACTIVATION; BORYLATION; REDUCTION; N-2; CO2;

D O I：

10.1002/anie.201710337

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Diphenyldiazomethane reacts with HB(C6F5)(2) and B(C6F5)(3), resulting in 1,1-hydroboration and adduct formation, respectively. The hydroboration proceeds via a concerted reaction involving initial formation of the Lewis adduct Ph2CN2BH(C6F5)(2). The highly sensitive adduct Ph2CN2(B(C6F5)(3)) liberates N-2 and generates Ph2CB(C6F5)(3). DFT computations reveal that formation of Ph2CN2B(C6F5)(3) from carbene, N-2, and borane is thermodynamically favourable, suggesting steric frustration could preclude carbene-borane adduct formation and affect FLP-N-2 capture.

引用

页码：16588 / 16592

页数：5

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