Electrochemically mediated enantioselective reduction of chiral sulfoxides
Electrochemically mediated enantioselective reduction of chiral sulfoxides
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DOI：
10.1007/s00775-014-1215-5
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发表时间：
2015-03-01
影响因子：
3
通讯作者：
Bernhardt, Paul V.
中科院分区：
文献类型：
--
作者：
Chen, Kuan-I.;Challinor, Victoria L.;Bernhardt, Paul V.
来自荚膜红细菌的呼吸DMSO还原酶催化二甲基亚砜还原为二甲基硫醚。在本文中，我们已经利用这种钼酶作为对映选择性催化剂，从外消旋起始材料产生光学纯亚砜（甲基对甲苯基亚砜，甲基苯基亚砜和苯基乙烯基亚砜）。一个hexaminecobalt配合物在其二价氧化态作为工作电极和DMSO还原酶之间的电子转移的介质，不断重新激活营业额后的酶。在所有情况下，反应混合物的手性HPLC分析显示，S-亚砜被更迅速地还原，导致R异构体的富集或分离。
The respiratory DMSO reductase from Rhodobacter capsulatus catalyzes the reduction of dimethyl sulfoxide to dimethyl sulfide. Herein, we have utilized this Mo enzyme as an enantioselective catalyst to generate optically pure sulfoxides (methyl p-tolyl sulfoxide, methyl phenyl sulfoxide and phenyl vinyl sulfoxide) from racemic starting materials. A hexaaminecobalt coordination compound in its divalent oxidation state was employed as the mediator of electron transfer between the working electrode and DMSO reductase to continually reactivate the enzyme after turnover. In all cases, chiral HPLC analysis of the reaction mixture revealed that the S-sulfoxide was reduced more rapidly leading to enrichment or isolation of the R isomer.