title: Regiodivergent Lewis base-promoted O- to C-carboxyl transfer of furanyl carbonates.
abstract: Triazolinylidenes promote γ-selective C-carboxylation (up to 99 : 1 regioselectivity) in the O- to C-carboxyl transfer of furanyl carbonates in contrast to DMAP that promotes preferential α-C-carboxylation with moderate regiocontrol (typically 60 : 40 regioselectivity). The generality of this process is described and a simple mechanistic and kinetic model postulated to account for the observed regioselectivity.
authors: EaStCHEM, School of Chemistry, University of St Andrews, St Andrews, KY16 9ST, UK. ads10@st-andrews.ac.uk.
authors: Craig D
authors: CD
authors: Campbell
authors: Caroline
authors: C
authors: Joannesse
authors: Louis C
authors: LC
authors: Morrill
authors: Douglas
authors: D
authors: Philp
authors: Andrew D
authors: AD
authors: Smith
mesh_terms: D015761:4-Aminopyridine / Q000031:analogs & derivatives / Q000737:chemistry; D015107:4-Butyrolactone / Q000031:analogs & derivatives* / Q000737:chemistry; D002244:Carbon / Q000737:chemistry*; D002254:Carbonates / Q000737:chemistry*; D002384:Catalysis; D005663:Furans / Q000737:chemistry*; D007700:Kinetics; D058115:Lewis Bases; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D010100:Oxygen / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D002254:Carbonates; D005663:Furans; D058115:Lewis Bases; D002244:Carbon; C004511:butenolide; D015761:4-Aminopyridine; D015107:4-Butyrolactone; C003885:4-dimethylaminopyridine; D010100:Oxygen