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Copper(I)‐Catalyzed Regioselective Addition of Nucleophilic Silicon Across Terminal and Internal Carbon–Carbon Triple Bonds |
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| Authors: | Dr Chinmoy K Hazra Carolin Fopp Prof?Dr Martin Oestreich |
| Affiliation: | 1. Institut für Chemie, Technische Universit?t Berlin, Strasse des 17. Juni 115, 10623 Berlin (Germany), Fax: (+49)?30‐314‐28829;2. NRW Graduate School of Chemistry, Organisch‐Chemisches Institut, Westf?lische Wilhelms‐Universit?t Münster, Corrensstrasse 40, 48149 Münster (Germany) |
| 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. |
| Keywords: | alkynes copper regioselectivity silicon silylmetalation |
