Reactions of Fluoroalkanes with Mg-Mg Bonds: Scope, sp3 C-F/sp2 C-F Coupling and Mechanism

Greg Coates; Bryan J Ward; Clare Bakewell; Andrew J P White; Mark R Crimmin

doi:10.1002/chem.201804580

Reactions of Fluoroalkanes with Mg-Mg Bonds: Scope, sp³ C-F/sp² C-F Coupling and Mechanism

Chemistry. 2018 Nov 2;24(61):16282-16286. doi: 10.1002/chem.201804580. Epub 2018 Oct 5.

Authors

Greg Coates¹, Bryan J Ward¹, Clare Bakewell¹, Andrew J P White¹, Mark R Crimmin¹

Affiliation

¹ Department of Chemistry, Imperial College London, South Kensington, London, SW7 2AZ, UK.

Abstract

sp³ C-F Bonds of fluoroalkanes (7 examples; 1°, 2° and 3°) undergo addition to a low-valent Mg-Mg species generating reactive organomagnesium reagents. Further reactions with a series of electrophiles results in a net C-F to C-B, C-Si, C-Sn or C-C bond transformation (11 examples, diversity). The new reactivity has been exploited in an unprecedented one-pot magnesium-mediated coupling of sp³ C-F and sp² C-F bonds. Calculations suggest that the sp³ C-F bond activation step occurs by frontside nucleophilic attack of the Mg-Mg reagent on the fluoroalkane.

Keywords: C−F activation; cross-coupling; fluorocarbons; nucleophilic substitution; organomagnesium reagents.

Abstract

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