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Preparation of a Corannulene-functionalized Hexahelicene by Copper(I)-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units
Published on: September 18, 2016
Cobalt-Catalyzed Enantioselective Intermolecular C-H Carboamination with Racemic Allenes
Lenin Kumar Verdhi1, Nicolai Cramer1
1Laboratory of Asymmetric Catalysis and Synthesis, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne (EPFL)1015, Lausanne, Switzerland.
Abstract:
Enantioselective carboamination of allenes especially in conjunction with 3D-metal catalysis remains a significant challenge. We report chiral cyclopentadienyl cobaltIII-catalyzed regio-, chemo-, and enantioselective intermolecular C-H carboamination of racemic allenyl esters with N-phenoxyisobutyramides. The protocol offers an efficient approach for highly selective carboamination of allenes and affords synthetically valuable chiral γ-substituted-β-enamido esters with exceptional selectivities (up to 88% yield, >99:1 er, and >20:1 E/Z). Operating by a kinetic resolution pathway, the transformation was additionally optimized for recovery of enantioenriched allenes with high selectivity factors of up to 138. The utility was showcased by the resolution of methyl-(R,E)-(-)-tetradeca-2,4,5-trienoate, the male bean weevil pheromone.
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