105 / 2023-10-03 21:46:17

Fe-catalyzed phosphorylation of alcohols to construct C–P bonds：synthesis of phosphine oxides and alkylphosphines

Alcohols; P(O)-H compounds; Diphenylphosphine; Phosphine oxides; Alkylphosphines; Fe-catalyzed

New Technologies in Phosphorus Chemistry > 1) New reagents and methods in organophosphorus Chemistry

  Organophosphorus compounds play a crucial role in medicinal chemistry, agrochemistry, biological chemistry, and material chemistry. The development of efficient and versatile methods for their preparation is of current concern. Traditional synthetic methods  primarily rely on the transformation of halides RX to phosphine oxides or alkylphosphines  (involving the conversion of C-X bond to C-P(V) bond or C-P(III) bond). However, some of halides are toxic and environmentally unfriendly. Therefore, it is imperative and essential to establish a general, efficient and eco-friendly approach for constructing C-P(V) bond and C-P(III) bond from sustainable feedstocks.

  Alcohols are widely present in nature and possess the advantages of being cost-effective and having low toxicity. The utilization of alcohols for synthesizing phosphine oxides and alkylphosphines can circumvent the formation of detrimental halides. In recent decades, significant advancements have been made in transition metal catalysis for phosphorylating alcohols. However, previous methods also required relatively harsh conditions and specific alcohol structures. In addition, several researchers have recently explored metal-free catalytic reactions between alcohols and P(O)-H compounds , but these methods have only shown improved efficacy for certain alcohols with unique structures.

  Therefore, we have developed a practical and general approach for preparation of phosphine oxides and alkylphosphines through Fe-catalyzed cross-coupling reactions between simple alcohols and H-phosphine oxides. Thus, phosphine oxides could be obtained from the reaction of alcohols and P(O)-H compounds in one pot,and alkylphosphines could synthesized via the intermediate react with diphenylphosphine. This transformation offers a novel strategy for both C-P(V) bond and C-P(III) bond formation by cleaving  C-O bond.