The phosphinoboration of carbodiimides, isocyanates, isothiocyanates and CO2

Abstract

The transition metal-free addition of phosphinoboronate ester Ph₂PBpin (pin = 1,2-O₂C₂Me₄) to heterocumulenes including carbodiimides, isocyanates, isothiocyanates and carbon dioxide has been investigated. The corresponding 1,2-addition products were readily prepared at room temperature without the need of a catalyst or added base. Addition of methanol to the compounds derived from addition of Ph₂PBpin to carbodiimides, isocyanates, and isothiocyanates resulted in traditional hydrophosphination products. The methodology developed in this study provides a simple and elegant route for the generation of a wide range of functionalized phosphines. The phosphinoboronate ester Ph₂PBpin also selectively and reversibly adds to CO₂ at room temperature in a 1,2-manner.