Abstract
sp3C−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 sp3C−F and sp2C−F bonds. Calculations suggest that the sp3C−F bond activation step occurs by frontside nucleophilic attack of the Mg−Mg reagent on the fluoroalkane.
Highlights
Abstract: sp3C–F bonds of fluoroalkanes (7 examples; 1o, 2o and 3o) undergo addition to a low-valent Mg–Mg species generating reactive organomagnesium reagents
Slow progress in this area of research can, in part, be traced to the difficulties associated with the oxidative addition of sp3C–F bonds to transition metals
The resultant organomagnesium reagents can be used to transfer the alkyl group to boron, silicon, tin- and carbon-based electrophiles. The latter carbon–carbon bond forming reaction is an unprecedented example of a transition metal free cross-coupling reaction of two C–F bonds.[24]
Summary
Abstract: sp3C–F bonds of fluoroalkanes (7 examples; 1o, 2o and 3o) undergo addition to a low-valent Mg–Mg species generating reactive organomagnesium reagents. Electrophilic silylium ions,[5,6] and related species,[7,8,9] have proven remarkably adept catalysts for fluoride abstraction from fluoroalkanes, while a nucleophilic boryl anion has just emerged as a reagent capable of C–F cleavage of CF3H (HFC-23).[10] we, and others, demonstrated that sp3C–F bonds of fluoroalkanes undergo oxidative addition to single-site Al(I) complexes,[11,12,13] no further reactivity of the resultant group 13 reagents has been reported.
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