What is the difference between mono- and biphosphine ligands? Revealing the chemoselectivity in Pd-catalysed carbenation of bromonaphthalene

被引：1

作者：

Gong, Wenting ^{[1
]}

Fu, Dongmin ^{[2
,3
]}

Zhong, Kangbao ^{[4
,5
]}

Ni, Hao ^{[4
,5
]}

He, Xiaoqian ^{[4
,5
]}

Shan, Chunhui ^{[1
]}

Li, Rong ^{[1
]}

Lan, Yu ^{[2
,3
,4
,5
]}

机构：

[1] Chongqing Normal Univ, Coll Chem, Chongqing Key Lab Inorgan Funct Mat, Chongqing 401331, Peoples R China

[2] Zhengzhou Univ, Green Catalysis Ctr, Zhengzhou 450001, Henan, Peoples R China

[3] Zhengzhou Univ, Coll Chem, Zhengzhou 450001, Henan, Peoples R China

[4] Chongqing Univ, Sch Chem & Chem Engn, Chongqing 400030, Peoples R China

[5] Chongqing Univ, Chongqing Key Lab Theoret & Computat Chem, Chongqing 400030, Peoples R China

来源：

ORGANIC CHEMISTRY FRONTIERS | 2022年 / 9卷 / 18期

基金：

中国博士后科学基金; 中国国家自然科学基金;

关键词：

MIGRATORY INSERTION; HECK REACTION; MECHANISM; NICKEL; MONODENTATE; BROMOARENES; ACTIVATION; ORIGINS; ESTERS;

D O I：

10.1039/d2qo00910b

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Ligand-controlled chemoselectivity is an important topic in organometallic chemistry. In this work, DFT calculations were used to reveal the chemoselectivity of a Pd-catalysed three-component dearomative carbenation of bromonaphthalene with diazo compounds and allylborates. When a monophosphine ligand was used, ligand exchange with a diazo compound was favored by the release of a phosphine ligand. Therefore, a three-component coupling reaction could occur. However, when a biphosphine ligand was used, ligand exchange between the phosphine and the diazo compounds was difficult. Therefore, the Suzuki-Miyaura coupling product was observed in this case, without the participation of the carbene moiety.

引用

页码：4916 / 4923

页数：8

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[1] Distinct mechanisms for the oxidative addition of chloro-, bromo-, and lodoarenes to a bisphosphine palladium(0) complex with hindered ligands [J].