Golden Face of Phosphine: Cascade Reaction to Bridgehead Methanophosphocines by Intramolecular Double Hydroarylation.

ABSTRACT

Reported herein is the first example of a gold-catalyzed cyclization of bis(arylmethyl)ethynylphosphine oxides. This represents an original approach to bridgehead methanophosphocines 1, eight-membered heterocycles. Gold catalyst in combination with triflic acid activates alkyne and induces a double hydroarylation. Mechanistic studies suggest that the reaction proceeds stepwise, forming first the 1 H-isophosphinoline 2-oxide 5. Reduction and protection of the corresponding phosphine oxides 1 described herein also highlight the effectiveness of our approach to this new class of electron-rich ligands.