Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne , EPFL-SB-ISIC-LSPN, BCH5304, CH-1015 Lausanne , Switzerland.
J Am Chem Soc. 2019 Jul 24;141(29):11372-11377. doi: 10.1021/jacs.9b04551. Epub 2019 Jul 11.
The development of enantioselective pinacol rearrangement is extremely challenging due to the likelihood involvement of the carbenium intermediate that renders the stereochemical communication between catalyst and substrate difficult to achieve. Herein, we report chiral -triflyl phosphoramide-catalyzed enantioselective pinacol rearrangement of 1,2-tertiary diols and mechanistically related Meinwald rearrangement of tetrasubstituted epoxides for the synthesis of enantioenriched 2-alkynyl-2-arylcyclohexanones and 2,2-diarylcyclohexanones, respectively. Total synthesis of (+)-mesembrane featuring the catalytic enantioselective pinacol rearrangement as a key strategic step is also documented.
由于涉及可能的碳正离子中间体，使得催化剂和底物之间的立体化学通讯难以实现，因此对映选择性频哪醇重排的发展极具挑战性。在此，我们报告了手性 -三氟甲磺酸基磷酰胺催化的 1,2-叔二醇的对映选择性频哪醇重排以及四取代环氧化物的与机理相关的 Meinwald 重排，分别用于合成对映体富集的 2-炔基-2-芳基环己酮和 2,2-二芳基环己酮。（+）-mesembrane 的全合成也记录了作为关键战略步骤的催化对映选择性频哪醇重排。
