title: Palladium-Catalyzed, tert-Butyllithium-Mediated Dimerization of Aryl Halides and Its Application in the Atropselective Total Synthesis of Mastigophorene A.
abstract: A palladium-catalyzed direct synthesis of symmetric biaryl compounds from aryl halides in the presence of tBuLi is described. In situ lithium-halogen exchange generates the corresponding aryl lithium reagent, which undergoes a homocoupling reaction with a second molecule of the aryl halide in the presence of the palladium catalyst (1 mol %). The reaction takes place at room temperature, is fast (1 h), and affords the corresponding biaryl compounds in good to excellent yields. The application of the method is demonstrated in an efficient asymmetric total synthesis of mastigophorene A. The chiral biaryl axis is constructed with an atropselectivity of 9:1 owing to catalyst-induced remote point-to-axial chirality transfer.
authors.affiliation: Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
authors.forename: Jeffrey
authors.initials: J
authors.lastname: Buter
authors.affiliation: Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
authors.forename: Dorus
authors.initials: D
authors.lastname: Heijnen
authors.affiliation: Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
authors.forename: Carlos
authors.initials: C
authors.lastname: Vila
authors.affiliation: Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
authors.forename: Valentín
authors.initials: V
authors.lastname: Hornillos
authors.affiliation: Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
authors.forename: Edwin
authors.initials: E
authors.lastname: Otten
authors.affiliation: Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
authors.forename: Massimo
authors.initials: M
authors.lastname: Giannerini
authors.affiliation: Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands. a.j.minnaard@rug.nl.
authors.forename: Adriaan J
authors.initials: AJ
authors.lastname: Minnaard
authors.affiliation: Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands. b.l.feringa@rug.nl.
authors.forename: Ben L
authors.initials: BL
authors.lastname: Feringa
mesh_terms: D002384:Catalysis; D018360:Crystallography, X-Ray; D003517:Cyclopentanes / Q000138:chemical synthesis*; D019281:Dimerization; D006219:Halogens / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D012717:Sesquiterpenes / Q000138:chemical synthesis*
chemical_list: D003517:Cyclopentanes; D006219:Halogens; D009942:Organometallic Compounds; D012717:Sesquiterpenes; C500870:mastigophorene A; C046771:butyllithium; D010165:Palladium
keywords: aryl lithium compounds; homocoupling; palladium; symmetric biaryls; total synthesis