title: An enantioselective, intermolecular α-arylation of ester enolates to form tertiary stereocenters.
abstract: In transition-metal catalyzed, asymmetric α-arylation of carbonyl compounds, formation of tertiary centers with high enantioselectivity is a longstanding problem, due to easy enolization of the monoarylation products. Herein, we report such examples using a palladium catalyst supported by a new, (R)-H(8)-BINOL-derived monophosphine. Silyl ketene acetals, together with a weakly basic activator, were used as equivalents of ester anions, and they reacted smoothly with aryl triflates in excellent enantiomeric excess (ee). The usefulness of the reaction was demonstrated in a gram-scale synthesis of (S)-Naproxen in 92% ee.
authors.affiliation: Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore.
authors.forename: Zhiyan
authors.initials: Z
authors.lastname: Huang
authors.forename: Zheng
authors.initials: Z
authors.lastname: Liu
authors.forename: Jianrong Steve
authors.initials: JS
authors.lastname: Zhou
mesh_terms: D000080:Acetals / Q000737:chemistry; D000894:Anti-Inflammatory Agents, Non-Steroidal / Q000138:chemical synthesis; D002384:Catalysis; D004952:Esters / Q000737:chemistry; D005030:Ethylenes / Q000737:chemistry; D007659:Ketones / Q000737:chemistry; D009288:Naproxen / Q000138:chemical synthesis; D010165:Palladium / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000080:Acetals; D000894:Anti-Inflammatory Agents, Non-Steroidal; D004952:Esters; D005030:Ethylenes; D007659:Ketones; D010720:Phosphines; D009288:Naproxen; D010165:Palladium; C008223:ketene