Triphenylborane in Metal-Free Catalysis

The development and application of new organoboron reagents as Lewis acids in synthesis and metal-free catalysis have dramatically expanded over the past 20 years. In this context, we will show the recent uses of the simple and relatively weak Lewis acid BPh₃—discovered 100 years ago—as a metal-free catalyst for various organic transformations. The first part will highlight catalytic applications in polymer synthesis such as the copolymerization of epoxides with CO₂, isocyanate, and organic anhydrides to various polycarbonate copolymers and controlled diblock copolymers as well as alternating polyurethanes. This is followed by a discussion of BPh₃ as a Lewis acid component in the frustrated Lewis pair (FLP) mediated cleavage of hydrogen and hydrogenation catalysis. In addition, BPh₃-catalyzed reductive N-methylations and C-methylations with CO₂ and silane to value-added organic products will be covered as well along with BPh₃-catalyzed cycloadditions and insertion reactions. Collectively, this mini-review showcases the underexplored potential of commercially available BPh₃ in metal-free catalysis.