Rhodium-Catalyzed Methylthio Transfer Reaction between Ketone α-Positions: Reversible Single-Bond Metathesis of C-S and C-H Bonds

被引：24

作者：

Arisawa, Mieko ^{[1
]}

Suwa, Katsunori ^{[1
]}

Yamaguchi, Masahiko ^{[1
]}

机构：

[1] Tohoku Univ, Grad Sch Pharmaceut Sci, Dept Organ Chem, Sendai, Miyagi 9808578, Japan

来源：

ORGANIC LETTERS | 2009年 / 11卷 / 03期

关键词：

D O I：

10.1021/ol802619e

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

In the presence of a catalytic amount of RhH(PPh3)(4) and 1,2-bis(diphenylposphino)ethane (dppe), alpha-phenylthio ketones were methylthiolated with p-cyano-alpha-methylthioacetophenone giving alpha-phenylthio-alpha-methylthioketones. The methylthio transfer reaction between the ketone alpha-positions was reversible and at equilibrium, and the methylthio group was transferred in preference to the phenylthio group. The reaction of tertiary alkyl methylthiomethyl ketones proceeded in high yields; the reaction of diastereomeric 4-(tert-butyl)-2-phenylthiocyclohexanones gave an axial 2-methylthiolated product.

引用

页码：625 / 627

页数：3

共 20 条

[1] Copper(I)-promoted palladium-catalyzed cross-coupling of unsaturated tri-n-butylstannane with heteroaromatic thioether [J].