title: Access to Enantiopure Triarylmethanes and 1,1-Diarylalkanes by NHC-Catalyzed Acylative Desymmetrization.
abstract: We present herein an unprecedented, efficient and enantioselective synthesis of triarylmethanes and 1,1-diarylalkanes through N-heterocyclic carbene-catalyzed acylative desymmetrization of bisphenols. This method utilizes readily available substrates, reagents and a simple procedure to deliver the valuable products in excellent enantiopurity. DFT calculations reveal that the selectivity is governed by the C-C bond cleavage step of the tetrahedral intermediate leading to the ester product. A transition state model featuring a combination of intramolecular hydrogen bond and steric effect is developed to explain the enantioselectivity.
authors.affiliation: Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore.
authors.forename: Shenci
authors.initials: S
authors.lastname: Lu
authors.affiliation: Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore.
authors.forename: Xiaoxiao
authors.initials: X
authors.lastname: Song
authors.affiliation: Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore.
authors.forename: Si Bei
authors.initials: SB
authors.lastname: Poh
authors.affiliation: Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore.
authors.forename: Hui
authors.identifier: http://orcid.org/0000-0002-0435-6763
authors.initials: H
authors.lastname: Yang
authors.affiliation: Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore.
authors.forename: Ming Wah
authors.initials: MW
authors.lastname: Wong
authors.affiliation: Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore.
authors.forename: Yu
authors.identifier: http://orcid.org/0000-0002-2944-1315
authors.initials: Y
authors.lastname: Zhao
keywords: 1,1-diarylalkanes; N-heterocycles; acylation; carbenes; desymmetrization