Abstract

Improved methods for the preparation of methylene-bridged diphosphine ligands are described. Both enantiomers of the key intermediate tert-butylmethylphosphine–borane were prepared via resolution or by the conversion of one enantiomer into the opposite enantiomer. The precursor borane complexes of bis( tert-butylmethylphosphino)methane ( t-Bu-MiniPHOS), bis((1,1,3,3-tetramethylbutyl)methylphosphino)methane ( t-Oct-MiniPHOS), and ( tert-butylmethylphosphino)(di- tert-butylphosphino)methane (trichickenfootphos) were prepared in good yields and enantiopure form.

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