Department of Chemistry, University of South Florida, 4202 East Fowler Avenue, CHE 205A, Tampa, FL, 33620, USA.
Department of Chemistry, Texas A&M University, College Station, TX, 77843, USA.
Angew Chem Int Ed Engl. 2017 Feb 20;56(9):2454-2458. doi: 10.1002/anie.201611602. Epub 2017 Jan 23.
Axially chiral cyclohexylidene oxime ethers exhibit unique chirality because of the restricted rotation of C=N. The first catalytic enantioselective synthesis of novel axially chiral cyclohexylidene oximes has been developed by catalytic desymmetrization of 4-substituted cyclohexanones with O-arylhydroxylamines and is catalyzed by a chiral BINOL-derived strontium phosphate with excellent yields and good enantioselectivities. In addition, chiral BINOL-derived phosphoric acid catalyzed dynamic kinetic resolution of α-substituted cyclohexanones has been performed and yields versatile intermediates in high yields and enantioselectivities.
轴手性环己基亚硝醚由于 C=N 的限制旋转而表现出独特的手性。通过手性 BINOL 衍生的磷酸锶催化 4-取代环己酮与 O-芳基羟胺的不对称去对称化，首次发展了新型轴手性环己基亚硝醚的催化对映选择性合成，具有优异的收率和良好的对映选择性。此外，手性 BINOL 衍生的磷酸催化了 α-取代环己酮的动态动力学拆分，以高产率和高对映选择性得到了多种中间体。
