Ruthenium-catalyzed oxidation of alkenes, alkynes, and alcohols to organic acids with aqueous hydrogen peroxide
Ruthenium-catalyzed oxidation of alkenes, alkynes, and alcohols to organic acids with aqueous hydrogen peroxide
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DOI：
10.1002/asia.200600091
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发表时间：
2006-09-01
影响因子：
4.1
通讯作者：
Yu, Wing-Yiu
中科院分区：
文献类型：
--
作者：
Che, Chi-Ming;Yip, Wing-Ping;Yu, Wing-Yiu
本文报道了一种以过氧化氢水溶液为末端氧化剂，[（Me（3）tacn）（CF_3CO_2）（2）Ru-III（OH_2）] CF_3CO_2（1; Me（3）tacn= 1，4，7-三甲基-1，4，7-三氮杂环壬烷）为催化剂，催化氧化烯烃、炔和醇为有机酸的反应，产率超过80%。对于环己烯氧化为己二酸，1的负载量可降低至0.1mol%。在1摩尔规模上，用1摩尔%的1氧化环己烯、环辛烯和1-辛醇分别产生己二酸（124 g，85%产率）、辛二酸（158 g，91%产率）和1-辛酸（129 g，90%产率）。氧化性C=C键断裂反应通过形成顺式-和反式-二醇中间体进行，所述中间体通过C-C键断裂进一步氧化成羧酸。
A protocol that adopts aqueous hydrogen peroxide as a terminal oxidant and [(Me(3)tacn)(CF3CO2)(2)Ru-III(OH2)]CF3CO2 (1; Me(3)tacn=1,4,7-trimethyl-1,4,7-triazacyclononane) as a catalyst for oxidation of alkenes, alkynes, and alcohols to organic acids in over 80% yield is presented. For the oxidation of cyclohexene to adipic acid, the loading of 1 can be lowered to 0.1 mol%. On the one-mole scale, the oxidation of cyclohexene, cyclooctene, and 1-octanol with 1 mol % of 1 produced adipic acid (124 g, 85% yield), suberic acid (158 g, 91% yield), and 1-octanoic acid (129 g, 90% yield), respectively. The oxidative C=C bond-cleavage reaction proceeded through the formation of cis- and traps-diol intermediates, which were further oxidized to carboxylic acids via C-C bond cleavage.