3 years ago

Trihydroborates and Dihydroboranes Bearing a Pentacoordinated Phosphorus Atom: Double Ring Expansion To Balance the Coordination States

Trihydroborates and Dihydroboranes Bearing a Pentacoordinated Phosphorus Atom: Double Ring Expansion To Balance the Coordination States
Nathan J. O'Brien, Romain Ramozzi, Naokazu Kano, Ryohei Uematsu, Keiji Morokuma
The first trihydroborate bearing a pentacoordinated phosphorus atom was synthesized as a new P−B bonded compound. Hydride abstraction of the trihydroborate gave an intermediary dihydroborane, which showed hydroboration reactivity and was trapped with pyridine whilst maintaining the P−B bond. The dihydroborane underwent a rearrangement, which involved a double ring expansion to compensate for the unbalanced coordination states of the phosphorus and boron atoms, to give a new fused bicyclic phosphine-boronate. A lasting bond: The first trihydroborate bearing a pentacoordinated phosphorus atom was synthesized as a new P−B bonded compound. The corresponding dihydroborane, generated by the hydride abstraction, underwent a unique rearrangement. The rearrangement involved a double ring expansion, to compensate for the unbalanced coordination states of the phosphorus and boron atoms, to give a new fused bicyclic phosphine-boronate.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201701718

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