CATALYTIC ASYMMETRIC ADDITION OF POLYFUNCTIONAL DIALKYLZINCS TO BETA-STANNYLATED AND BETA-SILYLATED UNSATURATED ALDEHYDES

被引：93

作者：

OSTWALD, R ^{[1
]}

CHAVANT, PY ^{[1
]}

STADTMULLER, H ^{[1
]}

KNOCHEL, P ^{[1
]}

机构：

[1] UNIV MARBURG,FACHBEREICH CHEM,D-35032 MARBURG,GERMANY

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1994年 / 59卷 / 15期

关键词：

D O I：

10.1021/jo00094a027

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The addition of functionalized dialkylzincs to readily available beta-stannylated or beta-silylated unsaturated aldehydes in the presence of a catalytic amount of (1R,2R)-1,2-bis(trifluorosulfonamido)cyclohexane (8 mol%) provides chiral allylic alcohols in good yields (60-90%) and excellent enantioselectivity (usually in the range of 85-95% ee). The synthetic utility of these allylic alcohols as chiral building blacks is demonstrated. The gamma-stannylated allylic alcohols were submitted to a Stille coupling leading to polyfunctional allylic alcohols and gamma-alkoxy enones. A treatment with CuCN in N-methylpyrrolidone at 130 degrees C provided chiral unsaturated gamma-hydroxy nitriles. Finally, the desilylation of the gamma-silylated alcohols gave chiral allylic alcohols having a terminal double bond. The catalytic asymmetric addition was found to show an important inverse temperature dependance. A mechanism for this addition is proposed.

引用

页码：4143 / 4153

页数：11

共 62 条

[61] DIASTEREOSELECTIVITY OF THE CONJUGATE ADDITION OF ORGANOCOPPER REAGENTS TO GAMMA-ALKOXY ALPHA,BETA-UNSATURATED CARBONYL DERIVATIVES - IMPORTANCE OF THE REAGENT TYPE AND THE DOUBLE-BOND GEOMETRY [J].