中国科学院机构知识库网格
Chinese Academy of Sciences Institutional Repositories Grid
Mechanistic Investigation of Chiral Phosphoric Acid Catalyzed Asymmetric Baeyer-Villiger Reaction of 3-Substituted Cyclobutanones with H2O2 as the Oxidant

文献类型:期刊论文

作者Xu SM(徐森苗) ; Wang Z(王正) ; Li YX(李玉学) ; Zhang XM(张绪穆) ; Wang HM(汪海明) ; Ding KL(丁奎岭)
刊名Chem.-Eur. J.
出版日期2010
卷号16期号:10页码:3021-3035
ISSN号0947-6539
其他题名手性磷酸催化环丁酮衍生物与双氧水的不对称Baeyer-Villiger反应机理研究
通讯作者李玉学 ; 丁奎岭
英文摘要The mechanism of the chiral phosphoric acid catalyzed Baeyer-Villiger (B-V) reaction of cyclobutanones with hydrogen peroxide was investigated by using a combination of experimental and theoretical methods. Of the two pathways that have been proposed for the present reaction, the pathway involving a peroxyphosphate intermediate is not viable. The reaction progress kinetic analysis indicates that the reaction is partially inhibited by the gamma-factone product. Initial rate measurements suggest that the reaction follows Michaelis-Menten-type kinetics consistent with a bifunctional mechanism in which the catalyst is actively involved in both carbonyl addition and the subsequent rearrangement steps through hydrogen-bonding interactions with the reactants or the intermediate. High-level quantum chemical calculations strongly, support a two-step concerted mechanism in which the phosphoric acid activates the reactants or the intermediate in a synergistic manner through partial proton transfer. The catalyst simultaneously acts as a general acid, by increasing the electrophilicity of the carbonyl carbon, increases the nucleophilicity of hydrogen peroxide as a Lewis base in the addition step, and facilitates the dissociation of the OH group from the Criegee intermediate in the rearrangement step. The overall reaction is highly exothermic, and the rearrangement of the Criegee intermediate is the rate-determining step. The observed reactivity of this catalytic B-V reaction also results, in part, from the ring strain in cyclobutanones. The sense of chiral induction is rationalized by the analysis of the relative energies of the competing diastereomeric transition states, in which the steric repulsion between the 3-substituent of the cyclobutanone and the 3- and 3'-substituents of the catalyst, as well as the entropy and solvent effects, are found to be critically important.
学科主题金属有机化学
收录类别SCI
原文出处http://dx.doi.org/10.1002/chem.200902698
语种英语
WOS记录号WOS:000275943400011
公开日期2013-02-22
源URL[http://202.127.28.38/handle/331003/17879]  
专题上海有机化学研究所_金属有机化学国家重点实验室
推荐引用方式
GB/T 7714
Xu SM,Wang Z,Li YX,et al. Mechanistic Investigation of Chiral Phosphoric Acid Catalyzed Asymmetric Baeyer-Villiger Reaction of 3-Substituted Cyclobutanones with H2O2 as the Oxidant[J]. Chem.-Eur. J.,2010,16(10):3021-3035.
APA 徐森苗,王正,李玉学,张绪穆,汪海明,&丁奎岭.(2010).Mechanistic Investigation of Chiral Phosphoric Acid Catalyzed Asymmetric Baeyer-Villiger Reaction of 3-Substituted Cyclobutanones with H2O2 as the Oxidant.Chem.-Eur. J.,16(10),3021-3035.
MLA 徐森苗,et al."Mechanistic Investigation of Chiral Phosphoric Acid Catalyzed Asymmetric Baeyer-Villiger Reaction of 3-Substituted Cyclobutanones with H2O2 as the Oxidant".Chem.-Eur. J. 16.10(2010):3021-3035.

入库方式: OAI收割

来源:上海有机化学研究所

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