Design, Reactivities, and Practical Application of Dialkylzinc Hydride Ate Complexes Generated in Situ from Dialkylzinc and Metal Hydride. A New Methodology for Activation of NaH and LiH under Mild Conditions
Design, Reactivities, and Practical Application of Dialkylzinc Hydride Ate Complexes Generated in Situ from Dialkylzinc and Metal Hydride. A New Methodology for Activation of NaH and LiH under Mild Conditions
复制标题
DOI：
10.1021/ja9718477
复制
发表时间：
1997-11
影响因子：
15
通讯作者：
M. Uchiyama;S. Furumoto;M. Saito;Y. Kondo;T. Sakamoto*
中科院分区：
文献类型：
--
作者：
M. Uchiyama;S. Furumoto;M. Saito;Y. Kondo;T. Sakamoto*
我们设计了不同的二烷基锌氢化物配合物，由二烷基锌和金属氢化物制备，并研究了这些锌酸盐对二苯甲酮的反应性（和配体的转移倾向）。结果清楚地表明，二甲基锌盐是最强大的和选择性的锌酸盐的羰基还原。结果表明，该络合剂在温和条件下可有效地将酯、酰胺、醛、酮还原为相应的醇、胺，且产率较高。此外，该方法还被成功地用于α，β-不饱和羰基化合物的高选择性1，2-还原、环氧化物的区域选择性开环还原和醛在酮存在下的化学选择性还原。我们还讨论和澄清的活性物种和机制，这种还原使用非对映选择性还原的羰基化合物与相邻的手性中心。所以，这个re…
We designed various dialkylzinc hydride “ate” complexes, prepared from dialkylzinc and metal hydride, and investigated the reactivities (and the transference aptitude of ligands) of these zincates toward benzophenone. The results clearly reveal that dimethylzinc hydrides are the most powerful and selective zincates for the reduction of the carbonyl group. This complex reagent turned out to be effective for the reduction of esters and amides as well as aldehydes and ketones to the corresponding alcohols and amines with good to excellent yields under mild conditions. Furthermore, the method was successfully used for the highly selective 1,2-reduction of α,β-unsaturated carbonyl compounds, the regioselective ring-opening reduction of epoxides, and the chemoselective reduction of aldehydes in the presence of ketones. We also discuss and clarify the active species and the mechanism of this reduction using the diastereoselective reductions of some carbonyl compounds with an adjacent chiral center. Also, this re...