title: Positional Selectivity in C-H Functionalizations of 2-Benzylfurans with Bimetallic Catalysts.
abstract: Metal-catalyzed carbon-carbon bond-forming reactions are a mainstay in the synthesis of pharmaceutical agents. A long-standing problem plaguing the field of transition metal catalyzed C-H functionalization chemistry is control of selectivity among inequivalent C-H bonds in organic reactants. Herein we advance an approach to direct site selectivity in the arylation of 2-benzylfurans founded on the idea that modulation of cooperativity in bimetallic catalysts can enable navigation of selectivity. The bimetallic catalysts introduced herein exert a high degree of control, leading to divergent site-selective arylation reactions of both sp(2) and sp(3) C-H bonds of 2-benzylfurans. It is proposed that the selectivity is governed by cation-π interactions, which can be modulated by choice of base and accompanying additives [MN(SiMe3)2, M = K or Li·12-crown-4].
authors.affiliation: Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania , 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Jiadi
authors.initials: J
authors.lastname: Zhang
authors.affiliation: Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania , 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Sheng-Chun
authors.initials: SC
authors.lastname: Sha
authors.affiliation: Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania , 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Ana
authors.initials: A
authors.lastname: Bellomo
authors.affiliation: Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania , 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Nisalak
authors.initials: N
authors.lastname: Trongsiriwat
authors.affiliation: Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania , 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Feng
authors.initials: F
authors.lastname: Gao
authors.affiliation: Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania , 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Neil C
authors.initials: NC
authors.lastname: Tomson
authors.affiliation: Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania , 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Walsh
mesh_terms: D001593:Benzyl Compounds / Q000737:chemistry*; D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry; D005663:Furans / Q000737:chemistry*; D008670:Metals / Q000737:chemistry / Q000378:metabolism; D011789:Quantum Theory; D028561:Transition Elements / Q000737:chemistry*
chemical_list: D001593:Benzyl Compounds; D056831:Coordination Complexes; D005663:Furans; D008670:Metals; D028561:Transition Elements