Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm, Sweden.
Chemistry. 2010 Apr 6;16(13):4031-6. doi: 10.1002/chem.200903114.
Enzyme- and ruthenium-catalyzed dynamic kinetic asymmetric transformation (DYKAT) of bicyclic diols to their diacetates was highly enantio- and diastereoselective to give the corresponding diacetates in high yield with high enantioselectivity (99.9 % ee). The enantiomerically pure diols are accessible by simple hydrolysis (NaOH, MeOH), but an alternative enzyme-catalyzed ester cleavage was also used to give the trans-diol (R,R)-1 b in extremely high diastereomeric purity (trans/cis=99.9:0.1, >99.9 % ee). It was demonstrated that the diols can be selectively oxidized to the ketoalcohols in a ruthenium-catalyzed Oppenauer-type reaction. A formal enantioselective synthesis of sertraline from a simple racemic cis/trans diol 1 b was demonstrated.
酶和钌催化的双环二醇向其醋酸酯的动态动力学不对称转化（DYKAT）具有高度的对映选择性和非对映选择性，以高产率和高对映选择性（99.9%ee）得到相应的醋酸酯。通过简单水解（NaOH，MeOH）可以获得对映体纯的二醇，但也可以使用替代的酶催化酯裂解来获得反式二醇（R，R）-1b，其非对映体纯度极高（反式/顺式=99.9:0.1，>99.9%ee）。证明了二醇可以在钌催化的Oppenauer 型反应中选择性氧化为酮醇。从简单的外消旋顺/反二醇 1b 中进行了舍曲林的对映选择性全合成。
