Tetramethylphosphinane as a new secondary phosphine synthon

Abstract

Secondary phosphines are important building blocks in organic chemistry as their reactive P—H bond enables construction of more elaborate molecules. In particular, they can be used to construct tertiary phosphines that have widespread applications as organocatalysts, and as ligands in metal-complex catalysis. We report here a practical synthesis of the bulky secondary phosphine synthon 2,2,6,6-tetramethylphosphinane (TMPhos). Its nitrogen analogue tetramethylpiperidine, known for over a century, is used as a base in organic chemistry. We obtained TMPhos on a multigram scale from an inexpensive air-stable precursor, ammonium hypophosphite. TMPhos is also a close structural relative of di-tert-butylphosphine, a key component of many important catalysts. Herein we also describe the synthesis of key derivatives of TMPhos, with potential applications ranging from CO2 conversion to cross-coupling and beyond. The availability of a new core phosphine building block opens up a diverse array of opportunities in catalysis.