NDLI: Mechanistic insight into water-modulated cycloisomerization of enynyl esters using an Au(I) catalyst

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Yang, Xu Liu, Lingjun Bi, Siwei Liu, Yuxia Wang, Hongliang
Description	Author Affiliation: Liu Y ( College of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, P. R. China. siweibi@126.com.)
Abstract	By carrying out density functional theoretical calculations, we have performed a detailed mechanistic study of the Au(I)-catalyzed cycloisomerization of 1,6-enylnyl ester in a dry and wet dichloromethane solvent corresponding to hydrogenation and hydrolysis processes, respectively. The hydrogenation and hydrolysis mechanisms proposed in the previous literature starting from an enol ketal intermediate without the involvement of an Au(I) catalyst are found to involve high barriers and thus contradict the observed experimental findings. Alternatively, based on the theoretical calculations, a novel hydrogenation mechanism (i.e., Au-induced H-shift followed by enol intermediate self-promoted H-shift) and a hydrolysis mechanism (i.e., Au-stabilized H-shift/C–O binding with subsequent $H_{2}O-assisted$ H-shift) from an Au–enol ketal adduct corroborate the experimental observations. The calculated results indicate that under unchanged wet conditions, the formation of a hydrolysis product is not involved in the intermediacy of the hydrogenation product. However, if the initial dry environment is provided, a hydrogenation product will be afforded. And then it will relentlessly evolve into a hydrolysis product in the subsequent wet conditions. The present theoretical results not only rationalize the experimental observations well but provide new insight into the mechanisms of the significant water-mediated cycloisomerization reaction.
ISSN	14779226
Issue Number	12
Volume Number	44
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2015-03-28
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Esters Chemistry Gold Catalysis Cyclization Hydrogenation Hydrolysis Isomerism Thermodynamics Water Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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