Palladium(0)/Copper(I)-cocatalyzed cross-coupling of the zinc reagent of ethyl 3-bromo-3,3,-difluoropropionate with aryl (Alkenyl) halides:An efficient stereoselective synthesis of β-fluoro-α，β-unsaturated esters.

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	Palladium(0)/Copper(I)-cocatalyzed cross-coupling of the zinc reagent of ethyl 3-bromo-3,3,-difluoropropionate with aryl (Alkenyl) halides:An efficient stereoselective synthesis of β-fluoro-α，β-unsaturated esters.
	彭晟 ; 卿凤翎 ; 李毅群 ; 胡昌明
刊名	J. Org. Chem.
	2000
卷号	65 期号:3 页码:694-700
ISSN号	0022-3263
其他题名	钯(0)铜(I)催化3-溴-3,3-亚氟丙酸乙酯的锌试剂与芳基卤化物的偶联反应: 立体选择合成β-氟α,β-不饱和酯的有效方法
通讯作者	卿凤翎
英文摘要	Ethyl S-bromo-3, 3-diFluoropropionate (1) was prepared in an overall yield of 75% from the radical addition of dibromodifluoromethane to ethyl vinyl ether under Na^2^s20^4 initiation, followed by oxidation of the acetal with CaEo~acid. The treatment of 1 with active zinc dust in anhydrous DMF at room temperature produced the zinc reagent ZnBrCF^2CH^2CO^2C^2H^5 (2). The cross coupling of the zinc reagent 2 with aryl (alkenyl) halides (R-X) in DM7 using Pd(0)- Cu(I) as cocatalyst stereoselectively provided the β－fluoro-α,β-unsaturated esters (RCF＝CHCO^2C^2H^5 4) directly and in moderate yields. An E/Z ratio ranging from 3:2 to 1:0 was observed. This is the first example that Cu(I) can improve the selectivity of the cross-coupling reaction. Mechanistic studies revealed that zinc reagent 2 underwent stereoselective elimination to produce (Z)- 1-fluoro-2-(ethoxycarbonyl)-ethenylzinc reagent 6, and then the cross-coupling of 6 with aryl(alkenyl) halides under palladium-(0) catalysis afforded the β-f1uoro-α，β-unsaturated esters 4.
学科主题	氟化学 ; 金属有机化学
收录类别	SCI
原文出处	http://dx.doi.org/10.1021/jo991276w
语种	英语
公开日期	2013-02-22
内容类型	期刊论文
源URL	[http://202.127.28.38/handle/331003/17459]
专题	上海有机化学研究所_中科院有机氟化学重点实验室
推荐引用方式 GB/T 7714	彭晟,卿凤翎,李毅群,等. Palladium(0)/Copper(I)-cocatalyzed cross-coupling of the zinc reagent of ethyl 3-bromo-3,3,-difluoropropionate with aryl (Alkenyl) halides:An efficient stereoselective synthesis of β-fluoro-α，β-unsaturated esters.[J]. J. Org. Chem.,2000,65(3):694-700.
APA	彭晟,卿凤翎,李毅群,&胡昌明.(2000).Palladium(0)/Copper(I)-cocatalyzed cross-coupling of the zinc reagent of ethyl 3-bromo-3,3,-difluoropropionate with aryl (Alkenyl) halides:An efficient stereoselective synthesis of β-fluoro-α，β-unsaturated esters..J. Org. Chem.,65(3),694-700.
MLA	彭晟,et al."Palladium(0)/Copper(I)-cocatalyzed cross-coupling of the zinc reagent of ethyl 3-bromo-3,3,-difluoropropionate with aryl (Alkenyl) halides:An efficient stereoselective synthesis of β-fluoro-α，β-unsaturated esters.".J. Org. Chem. 65.3(2000):694-700.