title: Copper(I)-catalyzed regioselective addition of nucleophilic silicon across terminal and internal carbon-carbon triple bonds.
abstract: The copper(I) alkoxide-catalyzed release of a silicon-based cuprate reagent from a silicon-boron pronucleophile is applied to the addition across carbon-carbon triple bonds. Commercially available CuBr⋅Me2S was found to be a general precatalyst that secures high regiocontrol for both aryl- and alkyl-substituted terminal as well as internal alkynes. The solvent greatly influences the regioisomeric ratio, favoring the linear regioisomer with terminal acceptors. This facile protocol even allows for the transformation of internal acceptors with remarkable levels of regio- and diastereocontrol.
authors: Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin (Germany), Fax: (+49) 30-314-28829; NRW Graduate School of Chemistry, Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster (Germany).
authors: Chinmoy K
authors: CK
authors: Hazra
authors: Carolin
authors: C
authors: Fopp
authors: Martin
authors: M
authors: Oestreich
keywords: alkynes; copper; regioselectivity; silicon; silylmetalation