首页|Carbonylation Reactions of a Metallapentalyne:Synthesis of Its Ester and Amide Derivatives

Carbonylation Reactions of a Metallapentalyne:Synthesis of Its Ester and Amide Derivatives

扫码查看
原文链接
  • 万方数据
  • 维普
Carbonylation reactions are a valuable synthetic method to construct carbonyl compounds and carbonylation reactions of aryl halides stand out as a highly significant tool for generating carbonyl substituted arenes.However,the important reactions have never been realized in aromatic metallacycles.Herein,we present the first carbonylation reactions of metallaaromatics,specifically alkoxycar-bonylation and aminocarbonylation reactions of an osmapentalyne.During the carbonylation process,the electronic and steric prop-erties of nucleophiles are regarded as critical factors.The alcohols with bulky substituents(isopropanol)require more reaction time and tert-butyl alcohol is inert in the reaction.Comparatively,amines,being stronger nucleophiles,exhibit divergent behaviors.Bulky amines undergo aminocarbonylation,whereas small amines prefer direct nucleophilic additions.Control experiments revealed that the intermediate derived from coupling of metal carbyne with CO plays a significant role in the carbonylation reaction.According to these observations,a divergent pathway for the reaction is proposed.Furthermore,the photophysical properties of these carbon-yl-functionalized osmapentalene complexes are studied,and the maximum absorption peak of compound with a carboxylic group ex-hibits a significant red-shift due to the smaller HOMO-LUMO gap.These findings contribute to expanding the reactivity of metallaaromatics and offer new opportunities for the synthesis of carbonyl-functionalized metallacycles.

Carbonylation reactionsMetal carbyneAromaticityCarbon monoxideMetallacycle

Yongfa Zhu、Dafa Chen、Ming Luo、Haiping Xia

展开 >

State Key Laboratory of Physical Chemistry of Solid Surfaces,Collaborative Innovation Center of Chemistry for Energy Materials(iChEM),College of Chemistry and Chemical Engineering,Xiamen University,Xiamen,Fujian 361005,China

Shenzhen Grubbs Institute,Department of Chemistry,Southern University of Science and Technology,Shenzhen,Guangdong 518055,China

2024

10.1002/cjoc.202400409

中国化学(英文版)
中国化学会 上海有机化学研究所

中国化学(英文版)

CSTPCD
影响因子：0.848
ISSN：1001-604X
年,卷(期)：2024.42(22)