Details

Autor(en) / Beteiligte

• Gutierrez, Osvaldo
• Tellis, John C
• Primer, David N
• Molander, Gary A
• Kozlowski, Marisa C

Titel

Nickel-Catalyzed Cross-Coupling of Photoredox-Generated Radicals: Uncovering a General Manifold for Stereoconvergence in Nickel-Catalyzed Cross-Couplings

Ist Teil von

• Journal of the American Chemical Society, 2015-04, Vol.137 (15), p.4896-4899

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2015

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The cross-coupling of sp3-hybridized organo­boron reagents via photoredox/​nickel dual catalysis represents a new paradigm of reactivity for engaging alkyl­metallic reagents in transition-metal-catalyzed processes. Reported here is an investigation into the mechanistic details of this important transformation using density functional theory. Calculations bring to light a new reaction pathway involving an alkyl­nickel­(I) complex generated by addition of an alkyl radical to Ni(0) that is likely to operate simultaneously with the previously proposed mechanism. Analysis of the enantio­selective variant of the transformation reveals an unexpected manifold for stereo­induction involving dynamic kinetic resolution (DKR) of a Ni­(III) intermediate wherein the stereo­determining step is reductive elimination. Furthermore, calculations suggest that the DKR-based stereo­induction manifold may be responsible for stereo­selectivity observed in numerous other stereo­convergent Ni-catalyzed cross-couplings and reductive couplings.