Desymmetrization of <i>meso-</i>Dicarbonatecyclohexene with β-Hydrazino Carboxylic Esters via a Pd-Catalyzed Allylic Substitution Cascade
Kai Xu, Yan Zheng, Yong Ye, Delong Liu, Wanbin Zhang
Abstract
-dicarbonatecyclohexene with β-hydrazino carboxylic esters has been achieved via a RuPHOX/Pd-catalyzed allylic substitution cascade for the construction of chiral hexahydrocinnoline derivatives with high performance. Mechanistic studies reveal that the reaction exploits a pathway different from that of our previous work and that the first nitrogen nucleophilic process is the rate-determining step. The protocol could be conducted on a gram scale without any loss of catalytic behavior, and the corresponding chiral hexahydrocinnolines can undergo diverse transformations.
Topics & Concepts
DesymmetrizationChemistryAllylic rearrangementCatalysisNucleophileCascadeCombinatorial chemistryCarboxylic acidNucleophilic substitutionMedicinal chemistryOrganic chemistryEnantioselective synthesisChromatographySynthetic Organic Chemistry MethodsCyclopropane Reaction MechanismsAsymmetric Synthesis and Catalysis