A family of cis-macrocyclic diphosphines: modular, stereoselective synthesis and application in catalytic CO₂/ethylene Coupling

A family of cis-macrocyclic diphosphines was prepared in just three steps from white phosphorus and commercial materials using a modular synthetic approach. Alkylation of bicyclic diphosphane 3,4,8,9-tetramethyl-1,6-diphosphabicyclo(4.4.0)deca-3,8-diene, or P₂(dmb)₂ , produced phosphino-phosphonium salts [R-P₂(dmb)₂]X, where R is methyl, benzyl and isobutyl, in yields of 90-96%. Treatment of these salts with organolithium or Grignard reagents yielded symmetric and unsymmetric macrocyclic diphosphines of the form cis-1-R-6-R′-3,4,8,9-tetramethyl-2,5,7,10-tetrahydro-1,6-DiPhospheCine, or R,R′-DPC, in which R′ is methyl, cyclohexyl, phenyl or mesityl, in yields of 46-94%. Alternatively, symmetric diphosphine Cy₂-DPC was synthesized in 74% yield from the dichlorodiphosphine Cl₂P₂(dmb)₂. As a first application, these cis-macrocyclic diphosphines were used as ligands in the nickel-catalyzed synthesis of acrylate from CO₂ and ethylene, for which they showed promising catalytic activity.National Science Foundation (U.S.) (Grant CHE-1111357)National Science Foundation (U.S.) (Grant CHE-1362118)National Science Foundation (U.S.) (Grant CHE-0946721