Reactivities of α-Oxo BMIDA Gold Carbenes Generated by Gold-Catalyzed Oxidation of BMIDA-Terminated Alkynes

被引：9

作者：

Zheng, Yang ^{[1
]}

Jiang, Jingxing ^{[3
]}

Li, Yue ^{[1
]}

Wei, Yongliang ^{[1
]}

Zhang, Junqi ^{[1
]}

Hu, Jundie ^{[4
]}

Ke, Zhuofeng ^{[3
]}

Xu, Xinfang ^{[2
]}

Zhang, Liming ^{[1
]}

机构：

[1] Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA

[2] Sun Yat sen Univ, Sch Pharmaceut Sci, Guangzhou 510006, Peoples R China

[3] Sun Yat sen Univ, Sch Mat Sci & Engn, PCFM Lab, Guangzhou 510275, Peoples R China

[4] Suzhou Univ Sci & Technol, Sch Mat Sci & Engn, Suzhou 215009, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2023年 / 62卷 / 17期

基金：

中国博士后科学基金;

关键词：

Alkynes; C-H Insertion; Carbenes; Gold Catalysis; alpha-Boryl Ketones; INTERMOLECULAR OXIDATION; EFFICIENT SYNTHESIS; CYCLIZATION; KETONES; REARRANGEMENT; INSERTION; ACCESS; BONDS;

D O I：

10.1002/anie.202218175

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

An oxidative strategy is reported to access alpha-oxo BMIDA gold carbenes directly from BMIDA-terminated alkynes. Besides offering expedient access to seldom studied boryl metal carbenes, these BMIDA gold carbene species undergo facile insertions into methyl, methylene, methine, and benzylic C-H bonds in the absence of the Thorpe-Ingold effect. They also undergo efficient OH insertion, cyclopropanation, and F-C alkylations. This chemistry provides rapid access to structurally diverse alpha-BMIDA ketones, which are scarcely documented. In combination with DFT studies, the role of BMIDA is established to be an electron-donating group that attenuates the high electrophilicity of the gold carbene center.

引用

页数：6

共 51 条

[1]

[Anonymous], 2011, ANGEW CHEM, V123, P3294

[2] BNC ISOSTERES OF CYCLOPROPANE AND A BORYLATED DIAZOESTER FROM DIAZO-COMPOUNDS AND (DIMETHYLAMINO)BIS(TRIFLUOROMETHYL)BORANE [J].

ANSORGE, A ;

BRAUER, DJ ;

BURGER, H ;

HAGEN, T ;

PAWELKE, G .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1993, 32 (03) :384-385

[3]

Ansorge A, 1993, ANGEW CHEM, V105, P429, DOI DOI 10.1002/ANGE.19931050319

[4] SYNTHESIS OF THE 1ST DISTILLABLE ALPHA-BORANYLDIAZOMETHANE - DIRECT EVIDENCE OF LITHIOBORANYLDIAZOMETHANE-LITHIOBORANYLISODIAZO-METHANE [(BCNN-,LI+)-(BNNC-,LI+)] REARRANGEMENT [J].

ARTHUR, MP ;

BACEIREDO, A ;

BERTRAND, G .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (15) :5856-5857

[5] Gold-Catalyzed Oxidative Alkyne Functionalization by N-O/S-O/C-O Bond Oxidants [J].

Bhunia, Sabyasachi ;

Ghosh, Partha ;

Patra, Snigdha Rani .

ADVANCED SYNTHESIS & CATALYSIS, 2020, 362 (18) :3664-3708

[6] Gold-Catalyzed Oxidative Cyclization/Aldol Addition of Homopropargyl Alcohols with Isatins [J].

Cai, Ju ;

Wang, Xin ;

Qian, Yu ;

Qiu, Lihua ;

Hu, Wenhao ;

Xu, Xinfang .

ORGANIC LETTERS, 2019, 21 (02) :369-372

[7]

Chen H., 2015, ANGEW CHEM, V127

[8] A Desulfonylative Approach in Oxidative Gold Catalysis: Regiospecific Access to Donor-Substituted Acyl Gold Carbenes [J].

Chen, Hongyi ;

Zhang, Liming .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (40) :11775-11779

[9] Synthesis of α-Borylated Ketones by Regioselective Wacker Oxidation of Alkenylboronates [J].

Corless, Victoria B. ;

Holownia, Aleksandra ;

Foy, Hayden ;

Mendoza-Sanchez, Rodrigo ;

Adachi, Shinya ;

Dudding, Travis ;

Yudin, Andrei K. .

ORGANIC LETTERS, 2018, 20 (17) :5300-5303

[10] A gold-catalysed fully intermolecular oxidation and sulfur-ylide formation sequence on ynamides [J].

Dos Santos, Mickael ;

Davies, Paul W. .

CHEMICAL COMMUNICATIONS, 2014, 50 (45) :6001-6004

← 1 2 3 4 5 6 →