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Updated: Jul 19, 2025

Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
Published on: March 20, 2017
Mimicking enzymatic cation-π interactions in hydrazide catalyst design: access to trans-decalin frameworks
Josephine M Warnica1, James L Gleason1
1Department of Chemistry, McGill University, 801 Sherbrooke W., Montreal, QC, H3A 0B8, Canada. jim.gleason@mcgill.ca.
Abstract:
Chiral bicyclic hydrazide organocatalysts have previously been shown to catalyze the cyclization of (Z)-polyene substrates with high enantioselectivity, but with poor selectivity for the corresponding (E)-polyenes. Here we demonstrate that diazapane carboxylates bearing terphenyl groups efficiently catalyze (E)-polyene bicyclization with enantioselectivities up to 94 : 6 er and with high diastereoselectivity for trans-decalin formation. The catalysts function by simultaneously initiating the cyclization via iminium ion formation and stabilizing intermediates/transition states by cation-π interactions.
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