Rhodium/Amine Dual Catalytic System for Reassembling CC Bonds of Conjugated Alkynes with Cyclopropenes via Cutting/ Insertion Cascade

被引：11

作者：

Chen, Jie ^{[1
,2
]}

Han, Jiabin ^{[2
]}

Zhang, Jian ^{[1
]}

Li, Ling ^{[1
]}

Zhang, Zhengyu ^{[2
]}

Yang, Yanhui ^{[2
]}

Jiang, Yaojia ^{[1
,2
]}

机构：

[1] Guizhou Univ, Lab Breeding Base Green Pesticide & Agr Bioengn, Key Lab Green Pesticide & Agr Bioengn, Minist Educ, Guiyang 550025, Peoples R China

[2] Nanjing Tech Univ, Inst Adv Synth, Sch Chem & Mol Engn, Nanjing 211816, Peoples R China

来源：

ACS CATALYSIS | 2022年 / 12卷 / 23期

基金：

中国国家自然科学基金;

关键词：

alkyne activation; cyclopropene; carbene; 1; 4-ketoaldehydes; amine; Rh(II) bicatalytic system; N-H INSERTION; RING-OPENING REACTION; ASYMMETRIC ORGANOCATALYSIS; STEREOSELECTIVE-SYNTHESIS; CYCLOPROPANATION; IDENTIFICATION; REARRANGEMENT; CARBENOIDS; RESISTANCE; PALLADIUM;

D O I：

10.1021/acscatal.2c03777

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Amines are powerful organocatalysts that are well-documented in catalyzing carbonyl compounds to realize trans-formations. However, they are rarely applied in alkyne activations. Herein, we disclose an efficient amine/Rh(II) dual catalytic system to reassemble the CC bond of conjugated alkynes with cyclopropenes, which enables construction of alpha-vinyldicarbonyl derivatives under very mild reaction conditions. Vinyl cyclopropylamines might be involved as key intermediates through ring-opening of cyclopropenes, catalytic amination of alkynes, and tandem cyclopropantion sequences in high atom and step-economies. This formal cutting/insertion cascade platform is compatible with a broad substrate scope including complex natural and unnatural molecules for late-stage functionalization.

引用

页码：14748 / 14753

页数：6

共 73 条

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