Effects of stereochemistry and β-substituents on the rates of vinylic SN2 reaction of hypervalent vinyl(phenyl)-λ3-iodanes with tetrabutylammonium halides

被引：15
|
作者：
Miyamoto, Kazunori [1 ]
Okubo, Takuji [1 ]
Hirobe, Masaya [1 ]
Kunishima, Munetaka [2 ]
Ochiai, Masahito [1 ]
机构：
[1] Univ Tokushima, Grad Sch Pharmaceut Sci, Tokushima 7708505, Japan
[2] Kanazawa Univ, Inst Med Pharmaceut & Hlth Sci, Fac Pharmaceut Sci, Kanazawa, Ishikawa 9201192, Japan
来源：
TETRAHEDRON | 2010年 / 66卷 / 31期
关键词：
S(N)2 reaction; Iodine; Hypervalent; Vinyliodane; Inversion; NUCLEOPHILIC-SUBSTITUTION; STEREOSELECTIVE-SYNTHESIS; ACTIVATED IODOSYLBENZENE; ALPHA-ELIMINATION; TRANSITION-STATE; IODONIUM SALTS; SP(2) CARBON; INVERSION; CONFIGURATION; GENERATION;
D O I：
10.1016/j.tet.2010.04.041
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
Both stereoisomers of beta-(2-phenylethoxy)vinyl-lambda(3)-iodane and (Z)-beta-aroyloxyvinyl-lambda(3)-iodane were prepared stereoselectively. These substituted vinyl-lambda(3)-iodanes undergo nucleophilic vinylic substitutions with n-Bu4NX (X=Cl, Br, I) under mild conditions, yielding vinyl halides. The observed inversion of configuration at the ipso vinylic carbon atom is compatible with a concerted vinylic S(N)2 mechanism. Kinetic measurements indicated that the rates for vinylic S(N)2 reaction of (Z)-vinyl-lambda(3)-iodane are greater than those of the E-isomer, probably because of the higher ground state energy of the Z-isomer. Electronic effects of beta-substituents of vinyl-lambda(3)-iodanes in the vinylic S(N)2 reaction are also discussed. (C) 2010 Elsevier Ltd. All rights reserved.
引用
收藏
页码：5819 / 5826
页数：8
相关论文
共 40 条
1234