title: Expanding the utility of Brønsted base catalysis: biomimetic enantioselective decarboxylative reactions.
abstract: As a result of the low reactivity of simple esters, the use of them as nucleophiles in direct asymmetric transformations is a long-standing challenge in synthetic organic chemistry. Nature approaches this difficulty through a decarboxylative mechanism, which is used for polyketide synthesis. Inspired by nature, we report guanidine-catalyzed biomimetic decarboxylative C-C and C-N bond-formation reactions. These highly enantioselective decarboxylative Mannich and amination reactions utilized malonic acid half thioesters as simple ester surrogates. It is proposed that nucleophilic addition precedes decarboxylation in the mechanism, which has been investigated in detail through the identification of intermediates by using electrospray ionization (ESI) mass-spectrometric analysis and DFT calculations.
authors.affiliation: Department of Chemistry, National University of Singapore (NUS), 3 Science Drive 3, 117543, Singapore.
authors.forename: Yuanhang
authors.initials: Y
authors.lastname: Pan
authors.forename: Choon Wee
authors.initials: CW
authors.lastname: Kee
authors.forename: Zhiyong
authors.initials: Z
authors.lastname: Jiang
authors.forename: Ting
authors.initials: T
authors.lastname: Ma
authors.forename: Yujun
authors.initials: Y
authors.lastname: Zhao
authors.forename: Yuanyong
authors.initials: Y
authors.lastname: Yang
authors.forename: Hansong
authors.initials: H
authors.lastname: Xue
authors.forename: Choon-Hong
authors.initials: CH
authors.lastname: Tan
mesh_terms: D032701:Biomimetics; D002244:Carbon / Q000737:chemistry; D002384:Catalysis; D019791:Guanidine / Q000737:chemistry*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D015394:Molecular Structure; D009584:Nitrogen / Q000737:chemistry
chemical_list: D002244:Carbon; D019791:Guanidine; D009584:Nitrogen