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The synthesis of phosphines is based on white phosphorus, which is usually converted to PCl 3 , to be afterwards substituted step by step in a non-atomic efficient manner. Herein, we describe an alternative efficient transition metal-mediated process to form asymmetrically substituted phosphines directly from white phosphorus (P 4 ). Thereby, P 4  is converted to [Cp*Fe(η 5 -P 5 )] ( 1 ) (Cp* = η 5 -C 5 (CH 3 ) 5 ) in which one of the phosphorus atoms is selectively functionalized to the 1,1-diorgano-substituted complex [Cp*Fe(η 4 -P 5 R′R″)] ( 3 ). In a subsequent step, the phosphine PR′R″R‴ (R′ ≠ R″ ≠ R‴ = alky, aryl) ( 4 ) is released by reacting it with a nucleophile R‴M (M = alkali metal) as racemates. The starting material  1  can be regenerated with P 4  and can be reused in multiple reaction cycles without isolation of the intermediates, and only the phosphine is distilled off.

Pentaphosphaferrocene-mediated synthesis of asymmetric organo-phosphines starting from white phosphorus