Borylation and Stannylation Reactions with Tuning of Lewis Acidity

A B(dan) moiety (dan=naphthalene-1,8-diaminato) of diminished boron-Lewis acidity has efficiently been installed into organic frameworks by three-component carboboration of alkenes under copper catalysis, where a Cu-B(dan) species, generated by chemoselective σ-bond metathesis between a copper catalyst and an unsymmetrical diboron [(pin)B-B(dan)], acts as a key intermediate. The Cu-B(dan) species has also turned out to serve as a B(dan) nucleophile to afford various dan-substituted organoboranes via borylative substitution of carbon electrophiles. Furthermore, borylation reactions with another Lewis acidity-diminished boron unit, B(aam) (aam=anthranilamidato), have become feasible by use of (pin)B-B(aam) or H-B(aam). The resulting dan/aam-substituted organoboranes have been demonstrated to undergo direct cross-coupling without prior acidic deprotection, regardless of their diminished boron-Lewis acidity. Synthesis of diverse organostannanes based upon copper-catalyzed carbostannylation and borylstannylation, in which Lewis acidity increment of a tin center facilitates the progress in some cases, have also been described.