METHYLCOPPER(I)-CATALYZED SELECTIVE CONJUGATE REDUCTION OF ALPHA,BETA-UNSATURATED CARBONYL-COMPOUNDS BY DIISOBUTYLALUMINUM HYDRIDE IN THE PRESENCE OF HEXAMETHYLPHOSPHORIC TRIAMIDE
METHYLCOPPER(I)-CATALYZED SELECTIVE CONJUGATE REDUCTION OF ALPHA,BETA-UNSATURATED CARBONYL-COMPOUNDS BY DIISOBUTYLALUMINUM HYDRIDE IN THE PRESENCE OF HEXAMETHYLPHOSPHORIC TRIAMIDE
复制标题
DOI：
10.1021/jo00354a027
复制
发表时间：
1986-02-21
影响因子：
3.6
通讯作者：
SAEGUSA, T
中科院分区：
文献类型：
--
作者：
TSUDA, T;HAYASHI, T;SAEGUSA, T
不饱和羰基化合物的选择性共轭还原(1，4-还原)是有机合成中的一项重要转化。尤其是高官能团化分子的选择性共轭还原是近年来研究的热点。开发了几种过渡金属氢化物试剂，包括由过渡金属化合物原位生成的试剂和传统的还原试剂。1以前我们曾报道，在六甲基磷三胺(HMPA)存在下，碘化亚铜催化氢化铝锂(LAH)共轭还原1/3-不饱和羰基化合物。2但还原效率和选择性不是很高。二异丁基氢化铝(DIBAH)是一种广泛应用于有机合成的还原剂，开发过渡金属化合物修饰的DIBAH的还原活性具有重要意义。本文报道了在HMPA(式1)存在下，甲基铜(I)催化的DIBAH对不饱和羰基化合物的高效选择性共轭还原反应。
Selective conjugate reduction (1, 4-reduction) of, ß-unsaturated carbonyl compounds is an important transformation in organicsynthesis. Especially, the selective conjugate reduction on highly functionalized molecules is a recent subject of considerable interest. Several transition-metal hydride reagents including those produced in situ from transition-metal compoundsand conventional reducing reagentshave been developed. 1 Previously we reported that cuprous iodide catalyzes conjugate reduction of,/3-unsaturated carbonyl compounds by lithium alu-minum hydride (LAH) in the presence of hexamethylphosphoric triamide (HMPA). 2 However, the efficiency and selectivity of the reduction were not very high. Diisobutylaluminum hydride (DIBAH) is a widely employed reducing reagent in organic synthesis, and it is interesting to exploit novel reducing reactivity of DIBAH modified by a transition-metal compound. Herein is reported me-thylcopper (I)-catalyzed highly efficient and selective con-jugate reduction of, ß-unsaturated carbonyl compounds by DIBAH in the presence of HMPA (eq 1).