均相[Ru(III)(Me3tacn)Cl3]催化的烯烃与过氧化氢水溶液的顺式二羟基化反应。

Homogeneous [Ru(III)(Me3tacn)Cl3]-catalyzed alkene cis-dihydroxylation with aqueous hydrogen peroxide.

作者信息

Yip Wing-Ping, Ho Chi-Ming, Zhu Nianyong, Lau Tai-Chu, Che Chi-Ming

机构信息

Department of Chemistry and Open Laboratory of Chemical Biology of the Institute of Molecular Technology for Drug Discovery and Synthesis, The University of Hong Kong, Pokfulam Road, Hong Kong, China.

出版信息

Chem Asian J. 2008 Jan 4;3(1):70-7. doi: 10.1002/asia.200700237.

DOI:10.1002/asia.200700237

PMID:17985328

Abstract

A simple and green method that uses [Ru(Me3tacn)Cl3] (1; Me3tacn = N,N',N''-trimethyl-1,4,7-triazacyclononane) as catalyst, aqueous H2O2 as the terminal oxidant, and Al2O3 and NaCl as additives is effective in the cis-dihydroxylation of alkenes in aqueous tert-butanol. Unfunctionalized alkenes, including cycloalkenes, aliphatic alkenes, and styrenes (14 examples) were selectively oxidized to their corresponding cis-diols in good to excellent yield (70-96%) based on substrate conversions of up to 100%. The preparation of cis-1,2-cycloheptanediol (119 g, 91% yield) and cis-1,2-cyclooctanediol (128 g, 92% yield) from cycloheptene and cyclooctene, respectively, on the 1-mol scale can be achieved by scaling up the reaction without modification. Results from Hammett correlation studies on the competitive oxidation of para-substituted styrenes (rho = -0.97, R = 0.988) and the detection of the cycloadduct [(Me3tacn)ClRuHO2(C8H14)]+ by ESI-MS for the 1-catalyzed oxidation of cyclooctene to cis-1,2-cyclooctanediol are similar to those of the stoichiometric oxidation of alkenes by cis-[(Me3tacn)(CF3CO2)Ru(VI)O2]+ through [3+2] cycloaddition (W.-P. Yip, W.-Y. Yu, N. Zhu, C.-M. Che, J. Am. Chem. Soc. 2005, 127, 14239).

摘要

一种简单且绿色的方法，使用[Ru(Me3tacn)Cl3]（1；Me3tacn = N,N',N''-三甲基-1,4,7-三氮杂环壬烷）作为催化剂、过氧化氢水溶液作为终端氧化剂以及氧化铝和氯化钠作为添加剂，在叔丁醇水溶液中对烯烃进行顺式二羟基化反应时效果良好。未官能化的烯烃，包括环烯烃、脂肪族烯烃和苯乙烯（14个实例），在高达100%的底物转化率下，以良好至优异的产率（70 - 96%）选择性地氧化为相应的顺式二醇。通过按比例扩大反应规模而无需修改，可分别由环庚烯和环辛烯以1摩尔规模制备顺式-1,2-环庚二醇（119克，产率91%）和顺式-1,2-环辛二醇（128克，产率92%）。对对位取代苯乙烯竞争氧化的哈米特相关性研究结果（ρ = -0.97，R = 0.988）以及通过电喷雾电离质谱（ESI-MS）检测环辛烯被1催化氧化为顺式-1,2-环辛二醇时的环加合物[(Me3tacn)ClRuHO2(C8H14)]+，与顺式[(Me3tacn)(CF3CO2)Ru(VI)O2]+通过[3 + 2]环加成对烯烃进行化学计量氧化的结果相似（W.-P. 叶、W.-Y. 余、N. 朱、C.-M. 车，《美国化学会志》2005年，127卷，14239页）。