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	Acid-Catalyzed Reactions of Twisted Amides in Water Solution: Competition between Hydration and Hydrolysis
	Wang, Binju ; Cao, Zexing ; Cao ZX(曹泽星)
	2011-09-07
关键词	ab initio calculations acid catalysis computer chemistry hydration hydrolysis twisted amides
英文摘要	The acid-catalyzed reactions of twisted amides in water solution were investigated by using cluster-continuum model calculations. In contrast to the previous widely suggested concerted hydration of the C=O group, our calculations show that the reaction proceeds in a practically stepwise manner, and that the hydration and hydrolysis channels of the C-N bond compete. The Eigen ion (H(3)O(+)) is the key species involved in the reaction, and it modulates the hydration and hydrolysis reaction pathways. The phenyl substitution in the twisted amide not only activates the N-CO bond, but also stabilizes the hydrolysis product through n(N)->pi(phenyl) delocalization, leading exclusively to the hydrolysis product of the ring-opened carboxylic acid. Generally, the twisted amides are more active than the planar amides, and such a rate acceleration results mainly from the increase in exothermicity in the first N-protonation step; the second step of the nucleophilic attack is less affected by the twisting of the amide bond. The present results show good agreement with the available experimental observations.; National Science Foundation of China[20733002, 20873105]; Ministry of Science and Technology[2011CB808504]
语种	英语
出版者	WILEY-BLACKWELL
内容类型	期刊论文
源URL	[http://dx.doi.org/doi:10.1002/chem.201101274]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Wang, Binju,Cao, Zexing,Cao ZX. Acid-Catalyzed Reactions of Twisted Amides in Water Solution: Competition between Hydration and Hydrolysis[J],2011.
APA	Wang, Binju,Cao, Zexing,&曹泽星.(2011).Acid-Catalyzed Reactions of Twisted Amides in Water Solution: Competition between Hydration and Hydrolysis..
MLA	Wang, Binju,et al."Acid-Catalyzed Reactions of Twisted Amides in Water Solution: Competition between Hydration and Hydrolysis".(2011).

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