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- Title
Insight into Isothiourea‐Catalyzed Enantioselective Addition of Saturated Esters to Iminium Ions.
- Authors
Liu, Si‐Cong; Li, Xue; Li, Shi‐Jun; Wei, Donghui
- Abstract
The possible mechanisms and origin of the selectivities of isothiourea‐catalyzed addition of saturated esters to iminium ions have been investigated by density functional theory. The favorable reaction pathway includes three stages: formation of an ammonium enolate intermediate, enantioselective addition of the ammonium enolate intermediate to the iminium ion, and dissociation of the catalyst to form the product. The enantioselective addition process is the stereoselectivity‐determining step, while the chemoselectivity‐determining step is included in the formation of the final product. The calculated energy barriers show that the chemoselectivity is thermodynamically controlled, and it depends on the polarities of the products and the nucleophilicities of the N atoms of the enamine reactant moieties of the intermediates. The origin of the stereoselectivity was investigated by non‐covalent interaction analysis of the key transition states. Hydrogen bonding interactions were identified as the determining factor for controlling the stereoselectivity. The obtained insight will be valuable for rational design of novel Lewis base organocatalyst‐promoted enantioselective addition reactions with special chemoselectivities.
- Subjects
HYDROGEN bonding interactions; IONS; ADDITION reactions; ACTIVATION energy; DENSITY functional theory
- Publication
Chemistry - An Asian Journal, 2019, Vol 14, Issue 23, p4322
- ISSN
1861-4728
- Publication type
Article
- DOI
10.1002/asia.201901163