Study on the reactive transient a-?3-iodanyl-acetophenone complex in the iodine(III)/PhI(I) catalytic cycle of iodobenzene-catalyzed a-acetoxylation reaction of acetophenone by electrospray ionization tandem mass spectrometry

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	Study on the reactive transient a-?3-iodanyl-acetophenone complex in the iodine(III)/PhI(I) catalytic cycle of iodobenzene-catalyzed a-acetoxylation reaction of acetophenone by electrospray ionization tandem mass spectrometry
	Wang HY(王昊阳) ; Zhou J(周娟) ; Guo YL(郭寅龙)
刊名	Rapid Commun. Mass Spectrom.
	2012
卷号	26 期号:6 页码:616-620
ISSN号	0951-4198
其他题名	电喷雾串联质谱研究碘苯催化的苯乙酮α-酰基化反应中活性三价碘复合物以及三价碘复合物/碘苯间的催化循环
通讯作者	王昊阳 ; 郭寅龙
英文摘要	RATIONALE: Hypervalent iodine compounds are important and widely used oxidants in organic chemistry. In 2005, Ochiai reported the PhI-catalyzed alpha-acetoxylation reaction of acetophenone by the oxidation of PhI with m-chloroperbenzoic acid (m-CPBA) in acetic acid. However, until now, the most critical reactive alpha-lambda(3)-iodine alkyl acetophenone intermediate (3) had not been isolated or directly detected. METHODS: Electrospray ionization tandem mass spectrometry (ESI-MS/ MS) was used to intercept and characterize the transient reactive alpha-lambda(3)-iodine alkyl acetophenone intermediate in the reaction solution. RESULTS: The trivalent iodine species was detected when PhI and m-CPBA in acetic acid were mixed, which indicated the facile oxidation of a catalytic amount of PhI(I) to the iodine(III) species by m-CPBA. Most importantly, 3.H+ was observed at m/z 383 from the reaction solution and this ion gave the protonated alpha-acetoxylation product 4.H+ at m/z 179 in MS/MS by an intramolecular reductive elimination of PhI. CONCLUSIONS: These ESI-MS/ MS studies showed the existence of the reactive alpha-lambda(3)-iodine alkyl acetophenone intermediate 3 in the catalytic cycle. Moreover, the gas-phase reactivity of 3.H+ was consistent with the proposed solution-phase reactivity of the alpha-lambda(3)-iodine alkyl acetophenone intermediate 3, thus confirming the reaction mechanism proposed by Ochiai. Copyright (C) 2012 John Wiley & Sons, Ltd.
学科主题	分析化学
收录类别	SCI
原文出处	http://dx.doi.org/10.1002/rcm.6145
语种	英语
WOS记录号	WOS:000300505400005
公开日期	2013-08-29
内容类型	期刊论文
源URL	[http://202.127.28.38/handle/331003/28667]
专题	上海有机化学研究所_分析化学研究室
推荐引用方式 GB/T 7714	Wang HY,Zhou J,Guo YL. Study on the reactive transient a-?3-iodanyl-acetophenone complex in the iodine(III)/PhI(I) catalytic cycle of iodobenzene-catalyzed a-acetoxylation reaction of acetophenone by electrospray ionization tandem mass spectrometry[J]. Rapid Commun. Mass Spectrom.,2012,26(6):616-620.
APA	王昊阳,周娟,&郭寅龙.(2012).Study on the reactive transient a-?3-iodanyl-acetophenone complex in the iodine(III)/PhI(I) catalytic cycle of iodobenzene-catalyzed a-acetoxylation reaction of acetophenone by electrospray ionization tandem mass spectrometry.Rapid Commun. Mass Spectrom.,26(6),616-620.
MLA	王昊阳,et al."Study on the reactive transient a-?3-iodanyl-acetophenone complex in the iodine(III)/PhI(I) catalytic cycle of iodobenzene-catalyzed a-acetoxylation reaction of acetophenone by electrospray ionization tandem mass spectrometry".Rapid Commun. Mass Spectrom. 26.6(2012):616-620.