title: Protecting group-free, selective cross-coupling of alkyltrifluoroborates with borylated aryl bromides via photoredox/nickel dual catalysis.
abstract: Orthogonal reactivity modes offer substantial opportunities for rapid construction of complex small molecules. However, most strategies for imparting orthogonality to cross-coupling reactions rely on differential protection of reactive sites, greatly reducing both atom and step economies. Reported here is a strategy for orthogonal cross-coupling wherein a mechanistically distinct activation mode for transmetalation of sp(3)-hybridized organoboron reagents enables C-C bond formation in the presence of various protected and unprotected sp(2)-hybridized organoborons. This manifold has the potential for broad application, because orthogonality is inherent to the activation mode itself. The diversification potential of this platform is shown in the rapid elaboration of a trifunctional lynchpin through various transition metal-catalyzed processes without nonproductive deprotection or functional group manipulation steps.
authors.affiliation: Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323; Process Chemistry Laboratories, Astellas Pharma Inc., Ibaraki 318-0001, Japan.
authors.forename: Yohei
authors.initials: Y
authors.lastname: Yamashita
authors.affiliation: Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323;
authors.forename: John C
authors.initials: JC
authors.lastname: Tellis
authors.affiliation: Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323; gmolandr@sas.upenn.edu.
authors.forename: Gary A
authors.initials: GA
authors.lastname: Molander
mesh_terms: D001881:Borates / Q000737:chemistry*; D001965:Bromides / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry; D002384:Catalysis; D020134:Catalytic Domain; D008956:Models, Chemical; D009532:Nickel / Q000737:chemistry*; D010084:Oxidation-Reduction; D010777:Photochemistry; D054852:Small Molecule Libraries / Q000138:chemical synthesis*
chemical_list: D001881:Borates; D001965:Bromides; D054852:Small Molecule Libraries; D002244:Carbon; D009532:Nickel
keywords: organotrifluoroborate; orthogonal cross-coupling; photoredox/nickel dual catalysis; single-electron transmetalation