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Catalytic Ester Metathesis Reaction and Its Application to Transfer Hydrogenation of Esters
ACS Catalysis ( IF 11.3 ) Pub Date : 2016-05-23 00:00:00 , DOI: 10.1021/acscatal.6b00827
Abhishek Dubey 1 , Eugene Khaskin 1
Affiliation  

We report a Ru-complex-catalyzed ester metathesis reaction where an unsymmetrical ester such as ethyl hexanoate can be transformed to a mixture of starting material, hexyl ethanoate, ethyl acetate, and hexyl hexanoate in equal proportions, as expected from a classical metathesis reaction with 0.2 mol % catalyst. A 20× excess of low boiling alcohol, such as ethanol, allows for the transfer of an acyl moiety to the sacrificial low boiling ethyl acetate product, while significantly increasing the functional group tolerance and substrate scope; yields of alcohols can reach 90%, which represents an attractive alternative to current high H2 pressure hydrogenation protocols for Ru-based ester reduction chemistry. Both reactions have not been reported previously in the field of Ru-catalyzed transformations of the ester functionality.

中文翻译:

催化酯复分解反应及其在酯转移加氢中的应用

我们报告了Ru络合物催化的酯复分解反应,其中不对称酯(如己酸乙酯)可以按等比例转化为起始原料,乙醇酸己酯,乙酸乙酯和己酸己酯的混合物,这是经典复分解反应所期望的。 0.2mol%的催化剂。20倍过量的低沸点醇(例如乙醇)可将酰基部分转移到牺牲性低沸点乙酸乙酯产品上,同时显着增加官能团的耐受性和底物范围;醇的收率可以达到90%,这是目前高H 2的诱人替代品钌基酯还原化学的高压氢化方案。先前在Ru催化的酯官能团的转化领域中尚未报道这两个反应。
更新日期:2016-05-23
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