Max-Planck-Institut für Kohlenforschung, Kaiser -Wilhelm-Platz 1, 45470 Mülheim an der Ruhr (Germany).
Angew Chem Int Ed Engl. 2014 Jul 28;53(31):8142-5. doi: 10.1002/anie.201400170. Epub 2014 Jun 24.
The hydrolytic ring opening of epoxides is an important biosynthetic transformation and is also applied industrially. We report the first organocatalytic variant of this reaction, exploiting our recently discovered activation of carboxylic acids with chiral phosphoric acids via heterodimerization. The methodology mimics the enzymatic mechanism, which involves an enzyme-bound carboxylate nucleophile. A newly designed phosphoric acid catalyst displays high stereocontrol in the desymmetrization of meso-epoxides. The methodology shows wide generality with cyclic, acylic, aromatic, and aliphatic substrates. We also apply our method in the first highly enantioselective anti-dihydroxylation of simple olefins.
环氧化物的水解开环是一种重要的生物合成转化，也在工业上得到应用。我们报告了这种反应的第一个有机催化变体，利用我们最近发现的通过杂二聚化用手性磷酸激活羧酸。该方法模拟了涉及酶结合的羧酸亲核体的酶促机制。一种新设计的磷酸催化剂在消旋的meso-环氧化物的不对称开环中显示出高立体选择性。该方法具有广泛的通用性，可适用于环状、非环状、芳香族和脂肪族底物。我们还将我们的方法应用于简单烯烃的首次高对映选择性反二羟化反应中。
