title: Catalytic activation of carbohydrates as formaldehyde equivalents for Stetter reaction with enones.
abstract: We disclose the first catalytic activation of carbohydrates as formaldehyde equivalents to generate acyl anions as one-carbon nucleophilic units for a Stetter reaction. The activation involves N-heterocyclic carbene (NHC)-catalyzed C-C bond cleavage of carbohydrates via a retro-benzoin-type process to generate the acyl anion intermediates. This Stetter reaction constitutes the first success in generating formal formaldehyde-derived acyl anions as one-carbon nucleophiles for non-self-benzoin processes. The renewable nature of carbohydrates, accessible from biomass, further highlights the practical potential of this fundamentally interesting catalytic activation.
authors.affiliation: Division of Chemistry & Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University , Singapore 637371, Singapore.
authors.forename: Junmin
authors.initials: J
authors.lastname: Zhang
authors.forename: Chong
authors.initials: C
authors.lastname: Xing
authors.forename: Bhoopendra
authors.initials: B
authors.lastname: Tiwari
authors.forename: Yonggui Robin
authors.initials: YR
authors.lastname: Chi
mesh_terms: D002241:Carbohydrates / Q000737:chemistry*; D002384:Catalysis; D005557:Formaldehyde / Q000138:chemical synthesis* / Q000737:chemistry; D006571:Heterocyclic Compounds / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D015394:Molecular Structure
chemical_list: D002241:Carbohydrates; D006571:Heterocyclic Compounds; D007659:Ketones; D005557:Formaldehyde; C030011:carbene; D008697:Methane