Ga‐catalyzed temperature‐dependent oxazolidinone/piperazine synthesis from phenyl aziridines involving a divergent ligand‐assisted mechanism

BILLACURA, Maria, LEWIS, Ryan, BRICKLEBANK, Neil, HAMILTON, Alexander and WHITEOAK, Christopher (2023). Ga‐catalyzed temperature‐dependent oxazolidinone/piperazine synthesis from phenyl aziridines involving a divergent ligand‐assisted mechanism. Advanced Synthesis & Catalysis.

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Abstract

Application of a binary Ga‐based catalyst system for the coupling of CO2 and aziridines to form oxazolidinones is presented. It has been possible to optimize the catalyst system for the selective formation of a single regioisomer, in excellent yield, under relatively mild reaction conditions. The optimized catalyst system has been successfully applied to a range of substituted aziridines derived from styrene oxide. It has been observed that aziridines bearing two aromatic substituents result in piperazine formation through an unexpected dimerization reaction. These piperazine products can be selectively formed in the absence of CO2 or are favored at lower reaction temperatures. A detailed DFT study into the reaction mechanism for the formation of both products has been carried out and an unusual ligand assistance in the case of oxazolidinone synthesis has been identified. More specifically, this ligand interaction promotes the initial ring‐opening of the aziridine and this work presents the first fully elucidated mechanism involving this intermediate.

Item Type:	Article
Additional Information:	** Article version: VoR ** From Wiley via Jisc Publications Router ** Licence for VoR version of this article: http://creativecommons.org/licenses/by-nc-nd/4.0/ **Journal IDs: issn 1615-4150; issn 1615-4169 **Article IDs: publisher-id: adsc202300537 **History: published_online 09-08-2023; rev-recd 18-07-2023; submitted 22-05-2023
Uncontrolled Keywords:	DFT study, Piperazines, Gallium catalysis, Aziridines, Oxazolidinones, Carbon dioxide
Identification Number:	https://doi.org/10.1002/adsc.202300537
SWORD Depositor:	Colin Knott
Depositing User:	Colin Knott
Date Deposited:	11 Aug 2023 10:27
Last Modified:	11 Oct 2023 12:16
URI:	https://shura.shu.ac.uk/id/eprint/32257

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