Insights Into the Gold(Ⅰ)-Catalyzed Cycloaddition of Alkynes with Allenes A Mechanistic DFT Study

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• 英文论文题名：Insights Into the Gold(Ⅰ)-Catalyzed Cycloaddition of Alkynes with Allenes: A Mechanistic DFT Study
• 论文作者：Qing Sun ; Xin Lu
• 英文论文作者：Qing Sun ; Xin Lu ; The State Key Laboratory for Physical Chemistry of Solid Surfaces and Center for Theoretical Chemistry ; Department of Chemistry ; College of Chemistry and Chemical Engineering ; Xiamen University
• 年：2016
• 作者机构：The State Key Laboratory for Physical Chemistry of Solid Surfaces and Center for Theoretical Chemistry, Department of Chemistry, College of Chemistry and Chemical Engineering,Xiamen University;
• 英文论文关键词：Gold(Ⅰ) ; Alkynes ; Allenes ; DFT
• 会议召开时间：2016-07-01
• 会议录名称：中国化学会第30届学术年会摘要集-第十八分会：电子结构理论方法的发展与应用
• 语种：英文
• 分类号：O621.251
• 学会代码：ZGHY
• 会议名称：中国化学会第30届学术年会-第十八分会 ; 电子结构理论方法的发展与应用
• 会议地点：中国辽宁大连
• 主办单位：中国化学会
• 学会名称：中国化学会
• 页数：1
• 文件大小：47k
• 原文格式：D
• 会议级别：全国

摘要

In recent years, there have been remarkable developments in gold(Ⅰ)-catalyzed organic synthesis processes including substrates like alkynes and allenes.~(1-3) Although, most previous studies focused on either alkynes or allenes as substrates, the reactions involving alkynes and allenes simultaneously are extremely rare. In this paper, we select multifunctional alkynes and electron-rich allenes from experiments, namely 2-(1-alkynyl)-2-alken-1-ones and N-allenamides, as research objects~4 and perform density functional theory(DFT) to elucidate the mechanisms. We consider the reaction pathways of alkynes with alkynes, allenes with allenes, alkynes with allenes. The theoretical study reveals the cycloaddition of alkynes with the proximal C=C bond of N-allenamides is the most favorable pathway. The substrate multifunctional alkynes is the key for cycloaddition of alkynes with allenes. Overall, we hope that the theoretical study gives some insights into the researches about new reactions of alkynes and allenes.
In recent years, there have been remarkable developments in gold(Ⅰ)-catalyzed organic synthesis processes including substrates like alkynes and allenes.~(1-3) Although, most previous studies focused on either alkynes or allenes as substrates, the reactions involving alkynes and allenes simultaneously are extremely rare.In this paper, we select multifunctional alkynes and electron-rich allenes from experiments, namely 2-(1-alkynyl)-2-alken-1-ones and N-allenamides, as research objects~4 and perform density functional theory(DFT) to elucidate the mechanisms.We consider the reaction pathways of alkynes with alkynes, allenes with allenes, alkynes with allenes.The theoretical study reveals the cycloaddition of alkynes with the proximal C=C bond of N-allenamides is the most favorable pathway.The substrate multifunctional alkynes is the key for cycloaddition of alkynes with allenes.Overall, we hope that the theoretical study gives some insights into the researches about new reactions of alkynes and allenes.

引文

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