1,1-Phosphaboration of C≡C and C=C bonds at gold

Cyril Theulier (1) , Yago García-Rodeja (2) , Nathalie Saffon‐merceron (3) , Karinne Miqueu (2) , Ghenwa Bouhadir (1) , Didier Bourissou (1)

1 LHFA - Laboratoire Hétérochimie Fondamentale et Appliquée
2 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux
3 ICT - Institut de Chimie de Toulouse

The phosphine-borane iPr2P(o-C6H4)BFXyl2 (Fxyl = 3,5-(F3C)2C6H3) was found to react with gold(i) alkynyl and vinyl complexes via an original 1,1-phosphaboration process. Zwitterionic complexes resulting from Au to B transmetallation have been authenticated as key intermediates. X-ray diffraction analyses show that the alkynyl-borate moiety remains pendant while the vinyl-borate is side-on coordinated to gold. According to DFT calculations, the phosphaboration then proceeds in a trans stepwise manner via decoordination of the phosphine, followed by anti nucleophilic attack to the π-CC bond activated by gold. The boron center acts as a relay and tether for the organic group.

Domaines: Chimie

Cyril Theulier, Yago García-Rodeja, Nathalie Saffon‐merceron, Karinne Miqueu, Ghenwa Bouhadir, et al.. 1,1-Phosphaboration of C≡C and C=C bonds at gold. Chemical Communications, 2021, 57 (3), pp.347-350. ⟨10.1039/d0cc06978g⟩. ⟨hal-03126727⟩