Utilization of Water as a Reagent in Regio- and Stereoselective Reactions
Utilization of Water as a Reagent in Regio- and Stereoselective Reactions
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在区域选择性和立体选择性反应中利用水作为试剂
DOI：
10.5059/yukigoseikyokaishi.63.18
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发表时间：
2005
影响因子：
0.2
通讯作者：
M. Tokunaga
中科院分区：
文献类型：
--
作者：
M. Tokunaga
水既是一种试剂又是一种溶剂，是合成有机化学中的一个重要课题。本文综述了过渡金属络合物催化水合和水解反应的最新进展。研究了Ru(II)催化水合反应直接转化1-炔烃为醛的反应。长期以来，人们一直认为水合作用遵循马尔科夫尼科夫的规则，将酮作为唯一的产物。反应机理研究表明，Ru(II)-偏二亚甲基络合物可能不参与当前的水合反应，但Ru(IV)-氢化物-偏亚甲基络合物参与了水合反应。还介绍了Ru(II)催化的氢胺化反应及其在杂环合成中的应用。本文还介绍了金属催化的末端环氧化物、烯基酯和醚类的水解反应。还研究了一些手性末端环氧化物和乙烯基醚的水解动力学拆分。
Utilization of water as a reagent as well as a solvent is an important topic in synthetic organic chemistry. This article describes recent progress of hydration and hydrolysis reactions catalyzed by transition metal complexes. Direct transformation of 1-alkynes into aldehydes by Ru (II) -catalyzed hydration has been developed. It has been long known as a textbook example that the hydration follows Markovnikov's rule to give ketones as a sole product. Mechanistic study of the transformation revealed that Ru (II) -vinylidene complexes presumably are not involved in the current hydration reaction, but Ru (IV) -hydride-vinylidene complexes are concerned. Ru (II) -catalyzed hydroamination and its application to heterocycle synthesis are also described. This paper also illustrates metal catalyzed hydrolysis of terminal epoxides, alkenyl esters and ethers. Hydrolytic kinetic resolution of some chiral terminal epoxides and vinyl ethers are also developed.