One-Pot Syntheses of Sterically Shielded Phosphorus Ligands by Selective Stepwise Nucleophilic Substitution at Triphenyl Phosphite

Abstract

A general, chlorophosphine-free procedure for the preparation of phosphonites, phosphinites and tertiary phosphines with at least one sterically demanding substituent has been developed. In this modular methodology, successive addition of stoichiometric amounts of carbanionic nucleophiles such as organyllithium reagents to P(OPh)₃ at low temperatures leads to selective stepwise substitution of the phenoxide leaving groups. Biphenyl-2-yl, 9-anthryl, and N-arylpyrrol-2-yl nucleophiles have been successfully employed for the first substitution step. Due to the steric shielding, the phosphorus derivatives are sufficiently stable for conventional aqueous work-up. Due to their phenoxide groups, diphenyl phosphonites and phenyl phosphinites usually possess sufficiently high melting points for the isolation by crystallization.

Key words

biaryls - ligands - metalations - phosphorus - pyrroles

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