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Updated: Aug 14, 2026
Preparation of Contiguous Bisaziridines for Regioselective Ring-Opening Reactions
Published on: July 28, 2022
Regiodivergent Rhodium Catalysis: Enantioselective Hydroacylation of 2-Azetines
Erin L Kuker1, Camryn E Wallace1, Stephanie A Corio2
1Department of Chemistry, University of California, Irvine, California92687-2025, United States.
This study demonstrates a new Rh-catalyzed hydroacylation of 2-azetines using specific ligands to control product formation. Ligand choice directs the reaction toward either chiral 2-acylazetidines or achiral 3-acylazetidines.
Area of Science:
- Organic Chemistry
- Catalysis
- Heterocyclic Chemistry
Background:
- 2-Azetines are strained heterocyclic compounds with limited functionalization methods.
- Hydroacylation reactions are crucial for forming carbon-carbon bonds.
- Controlling regioselectivity and enantioselectivity in these reactions remains a challenge.
Purpose of the Study:
- To develop a regio- and enantioselective Rh-catalyzed hydroacylation of 2-azetines.
- To explore the use of enecarbamates as coupling partners in this reaction.
- To understand the mechanism of ligand control over regioselectivity.
Main Methods:
- Rhodium-catalyzed hydroacylation of 2-azetines.
- Systematic variation of bisphosphine ligands (Josiphos, dppe).
- Mechanistic studies using distortion-interaction models.
Main Results:
- Selective synthesis of chiral 2-acylazetidines using electron-rich Josiphos ligands with high enantioselectivity.
- Selective synthesis of achiral 3-acylazetidines using biaryl bisphosphines like dppe.
- Successful application of enecarbamates as coupling partners, expanding reaction scope.
- Regiodivergence explained by distinct transition-state stabilization modes dictated by ligand properties.
Conclusions:
- Strategic ligand control enables precise regio- and enantioselective Rh-catalyzed hydroacylation of 2-azetines.
- This work introduces enecarbamates as novel substrates for hydroacylation.
- Ligand steric and electronic properties are key determinants of reaction outcome and mechanism.
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