Computational study of silver-catalyzed stereoselective hydroalkylation of alkynes: Pauli repulsion controlled Z/E selectivity

被引：24

作者：

Hu, Lingfei ^{[1
]}

Gao, Han ^{[1
]}

Hu, Yanlei ^{[1
]}

Lv, Xiangying ^{[1
]}

Wu, Yan-Bo ^{[2
,3
]}

Lu, Gang ^{[1
]}

机构：

[1] Shandong Univ, Sch Chem & Chem Engn, Key Lab Colloid & Interface Chem, Minist Educ, Jinan 250100, Shandong, Peoples R China

[2] Shanxi Univ, Inst Mol Sci, Key Lab Mat Energy Convers & Storage Shanxi Prov, Taiyuan 030006, Shanxi, Peoples R China

[3] Shanxi Univ, Inst Mol Sci, Minist Educ, Key Lab Chem Biol & Mol Engn, Taiyuan 030006, Shanxi, Peoples R China

来源：

CHEMICAL COMMUNICATIONS | 2021年 / 57卷 / 52期

基金：

中国国家自然科学基金;

关键词：

TERMINAL ALKYNES; CARBOXYLATION; ORIGIN; MODEL;

D O I：

10.1039/d1cc01917a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The mechanism and origin of stereoselectivity of silver-catalyzed hydroalkylation of alkynes were computationally investigated at the B3LYP-D3BJ/6-311+G(d,p)-SDD//B3LYP/6-31G(d)-LANL2DZ level. The complex of alkynyl trialkylboronate with cationic silver is a key intermediate, which triggers the rate- and stereoselectivity-determining 1,2-migration step. Energy decomposition analysis indicates that the difference of Pauli repulsion dominates the stereoselectivity.

引用

页码：6412 / 6415

页数：4

共 43 条

[1] Diastereodivergent Reductive Cross Coupling of Alkynes through Tandem Catalysis: Z- and E-Selective Hydroarylation of Terminal Alkynes [J].

Armstrong, Megan K. ;

Goodstein, Madison B. ;

Lalic, Gojko .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2018, 140 (32) :10233-10241

[2] Difunctionalization of C-C σ-Bonds Enabled by the Reaction of Bicyclo[1.1.0]butyl Boronate Complexes with Electrophiles: Reaction Development, Scope, and Stereochemical Origins [J].

Bennett, Steven H. ;

Fawcett, Alexander ;

Denton, Elliott H. ;

Biberger, Tobias ;

Fasano, Valerio ;

Winter, Nils ;

Aggarwal, Varinder K. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2020, 142 (39) :16766-16775

[3] Analyzing Reaction Rates with the Distortion/Interaction-Activation Strain Model [J].

Bickelhaupt, F. Matthias ;

Houk, Kendall N. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (34) :10070-10086

[4] AgN3-Catalyzed Hydroazidation of Terminal Alkynes and Mechanistic Studies [J].

Cao, Shanshan ;

Ji, Qinghe ;

Li, Huaizhi ;

Pang, Maolin ;

Yuan, Haiyan ;

Zhang, Jingping ;

Bi, Xihe .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2020, 142 (15) :7083-7091

[5] Z-Selective Olefin Synthesis via Iron-Catalyzed Reductive Coupling of Alkyl Halides with Terminal Arylalkynes [J].

Cheung, Chi Wai ;

Zhurkin, Fedor E. ;

Hu, Xile .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (15) :4932-4935

[6] Nickel-Catalyzed Enantioselective Conjunctive Cross-Coupling of 9-BBN Borates [J].

Chierchia, Matteo ;

Law, Chunyin ;

Morken, James P. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (39) :11870-11874

[7] Preparation of substituted enol derivatives from terminal alkynes and their synthetic utility [J].

DeBergh, John R. ;

Spivey, Kathleen M. ;

Ready, Joseph M. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (25) :7828-+

[8] Strain-Release-Driven Homologation of Boronic Esters: Application to the Modular Synthesis of Azetidines [J].

Fawcett, Alexander ;

Murtaza, Amna ;

Gregson, Charlotte H. U. ;

Aggarwal, Varinder K. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2019, 141 (11) :4573-4578

[9] Carbopalladation of C-C σ-bonds enabled by strained boronate complexes [J].

Fawcett, Alexander ;

Biberger, Tobias ;

Aggarwal, Varinder K. .

NATURE CHEMISTRY, 2019, 11 (02) :117-122

[10] The activation strain model and molecular orbital theory: understanding and designing chemical reactions [J].

Fernandez, Israel ;

Bickelhaupt, F. Matthias .

CHEMICAL SOCIETY REVIEWS, 2014, 43 (14) :4953-4967

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