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- Title
Hydrazide‐Catalyzed Polyene Cyclization: Asymmetric Organocatalytic Synthesis of cis‐Decalins.
- Authors
Plamondon, Samuel J.; Warnica, Josephine M.; Kaldre, Dainis; Gleason, James L.
- Abstract
Polyene cyclizations offer rapid entry into terpenoid ring systems. Although enantioselective cyclizations of (E)‐polyenes to form trans‐decalin ring systems are well precedented, highly enantioselective cyclizations of (Z)‐polyenes to form the corresponding cis‐decalins have not been reported. Here, we describe the first application of iminium catalysis to the initiation of polyene cyclizations. Ethyl 1,2‐diazepane‐1‐carboxylate catalyzes the cyclization of polyenes bearing enal initiators. Moreover, chiral bicyclic hydrazides catalyze the cyclizations of (Z)‐polyene substrates to form cis‐decalins with enantioselectivities of up to 97:3 er. DFT calculations suggest the catalysts promote the reaction by stabilizing positive charge as it develops during the bicyclization.
- Subjects
ASYMMETRIC synthesis; CATALYSIS; HYDRAZIDES; CATALYSTS
- Publication
Angewandte Chemie, 2020, Vol 132, Issue 1, p259
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201911952