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Metal‐Free Phosphorus‐Directed Borylation of C(sp 2 )−H Bonds

2021; Wiley; Volume: 61; Issue: 1 Linguagem: Inglês

10.1002/anie.202110102

1521-3773

Omar Sadek, Arnaud Le Gac, Nereida Hidalgo, Sonia Mallet‐Ladeira, Karinne Miqueu, Ghenwa Bouhadir, Didier Bourissou,

Catalytic C–H Functionalization Methods

Spectacular progress has recently been achieved in transition metal-catalyzed C-H borylation of phosphines as well as directed electrophilic C-H borylation. As shown here, P-directed electrophilic borylation provides a new, straightforward, and efficient access to phosphine-boranes. It operates under metal-free conditions and leverages simple, readily available substrates. It is applicable to a broad range of backbones (naphthyl, biphenyl, N-phenylpyrrole, binaphthyl, benzyl, naphthylmethyl) and gives facile access to various substitution patterns at boron (by varying the boron electrophile or post-derivatizing the borane moiety). NMR monitoring supports the involvement of P-stabilized borenium cations as key intermediates. DFT calculations reveal the existence and stabilizing effect of π-arene/boron interactions in the (biphenyl)(i-Pr)2 P→BBr2+ species.