The synthesis of 2,4-dienyl fluoroalkyl ketones by a tandem three-stage seuence of propargyl 2-fluoroalkylvinyl ether formation, Claisen rearrangement, and allene-to-conjugated diene isomerization

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	The synthesis of 2,4-dienyl fluoroalkyl ketones by a tandem three-stage seuence of propargyl 2-fluoroalkylvinyl ether formation, Claisen rearrangement, and allene-to-conjugated diene isomerization
	Peng WM(彭卫民) ; Zhu SZ(朱仕正)
刊名	Tetrahedron
	2003
卷号	59 期号:25 页码:4641-4649
ISSN号	0040-4020
其他题名	通过串联的2－氟烷基炔丙基烯基醚的制备，Claisen重排，联烯重排为共扼二烯三步反应合成2，4不饱和含氟烷基酮
通讯作者	朱仕正
英文摘要	A tandem three stages process to a series of trifluoromethyl and halodifluoromethyl 2,4-unsaturated ketones 4a-c is described.This process started with the preparation of 2-fluoroalkyl substituted propargyl vinyl ether 3a-d by treatment of a mixture of individual ethylα-per(poly)fluoroalkyl acetates la-d and propargyl alcohol 2 in CH^2Cl^2 with the mixed base (Na^2CO^3/TEA) at ambient temperature. When heated in toluene at 80℃, these ethers readily underwent a tandem propargyl-allenyl Claisen rearrangement and isomerization of the resultant 3,4-dienone to give 2,4-unsaturated fluoroalkyl ketones 4a-c (Z/E mixture). The reaction of ethyl α-per(poly)fluoroalkyl acetate I with l-phenyl propargyl alcohol 5 in refluxing CH^2Cl^2 in the presence of the mixed base (Na^2CO^3/TEA) directly afforded the cooesponding unsaturated fluoroalkyl ketone 6a-c in one pot. In the presence of NaH, the reaction of ethyl 3-halo-3-fluoroalkylacrylates 8a-b with 1,1-dimethyl propargyl alcohol 9 at -50℃ to 0℃ also gave the unsaturated Huoroalkyl ketones 10a-b in one pot. The difluorovinyl propargyl ether 11 prodnced by reduction of 2-bromodifluoromethyl substituted propargyl vinyl ether 3b rearranged in hot benzene to give the corresponding allene 12 bearing a gem-difluoromethylene group in the middle of the aliphatic chain.
学科主题	有机氟化学
收录类别	SCI
原文出处	http://dx.doi.org/10.1016/S0040-4020(03)00663-X
语种	英语
公开日期	2013-01-18
内容类型	期刊论文
源URL	[http://202.127.28.38/handle/331003/14300]
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	Peng WM,Zhu SZ. The synthesis of 2,4-dienyl fluoroalkyl ketones by a tandem three-stage seuence of propargyl 2-fluoroalkylvinyl ether formation, Claisen rearrangement, and allene-to-conjugated diene isomerization[J]. Tetrahedron,2003,59(25):4641-4649.
APA	彭卫民,&朱仕正.(2003).The synthesis of 2,4-dienyl fluoroalkyl ketones by a tandem three-stage seuence of propargyl 2-fluoroalkylvinyl ether formation, Claisen rearrangement, and allene-to-conjugated diene isomerization.Tetrahedron,59(25),4641-4649.
MLA	彭卫民,et al."The synthesis of 2,4-dienyl fluoroalkyl ketones by a tandem three-stage seuence of propargyl 2-fluoroalkylvinyl ether formation, Claisen rearrangement, and allene-to-conjugated diene isomerization".Tetrahedron 59.25(2003):4641-4649.