Mechanistic Investigation of Chiral Phosphoric Acid Catalyzed Asymmetric Baeyer-Villiger Reaction of 3-Substituted Cyclobutanones with H2O2 as the Oxidant

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	Mechanistic Investigation of Chiral Phosphoric Acid Catalyzed Asymmetric Baeyer-Villiger Reaction of 3-Substituted Cyclobutanones with H2O2 as the Oxidant
	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.
	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
内容类型	期刊论文
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.