title: Copper-Catalyzed Cross-Coupling of Silicon Pronucleophiles with Unactivated Alkyl Electrophiles Coupled with Radical Cyclization.
abstract: A copper-catalyzed C(sp3)-Si cross-coupling of aliphatic C(sp3)-I electrophiles using a Si-B reagent as the silicon pronucleophile is reported. The reaction involves an alkyl radical intermediate that also engages in 5-exo-trig ring closures onto pendant alkenes prior to the terminating C(sp3)-Si bond formation. Several Ueno-Stork-type precursors cyclized with excellent diastereocontrol in good yields. The base-mediated release of the silicon nucleophile and the copper-catalyzed radical process are analyzed by quantum-chemical calculations, leading to a full mechanistic picture.
authors.affiliation: Institut für Chemie, Technische Universität Berlin , Strasse des 17. Juni 115, 10623 Berlin, Germany.
authors.forename: Weichao
authors.initials: W
authors.lastname: Xue
authors.affiliation: Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn , Beringstrasse 4, 53115 Bonn, Germany.
authors.forename: Zheng-Wang
authors.initials: ZW
authors.lastname: Qu
authors.affiliation: Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn , Beringstrasse 4, 53115 Bonn, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Grimme
authors.affiliation: Institut für Chemie, Technische Universität Berlin , Strasse des 17. Juni 115, 10623 Berlin, Germany.
authors.forename: Martin
authors.initials: M
authors.lastname: Oestreich