Highly Chemoselective Transformation of Secondary Propargylic Alcohols with (EtO)(2)P(O)SH

A practical and environmentally friendly approach is presented for the efficient construction of propargyl organothiophosphates and allenyl organothiophosphates from easily prepared secondary propargylic alcohols and O, O-diethyl phosphorothioic acid [(EtO)(2)P(O)SH]. The reaction proceeds smoothly in moderate to excellent yields without additional acid promoters or additives under mild conditions with water as the only by-product. The divergent products are selectively obtained depending on substrates bearing different substituents on the aromatic ring. Notably, the developed reaction system can be scaled up to gram quantities.