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Copper-Catalyzed Cross-Coupling of Silicon Pronucleophiles with Unactivated Alkyl Electrophiles Coupled with Radical
Weichao Xue1, Zheng-Wang Qu2, Stefan Grimme2
1Institut für Chemie, Technische Universität Berlin , Strasse des 17. Juni 115, 10623 Berlin, Germany.
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.
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