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 s...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2017, Vol.8 (2), p.1463-1468
Main Authors: Knopf, Ioana, Tofan, Daniel, Beetstra, Dirk, Al-Nezari, Abdulaziz, Al-Bahily, Khalid, Cummins, Christopher C
Format: Article
Language:English
Subjects:
Carbon dioxide
Coupling
Ethylene
Ligands
Macrocyclic compounds
Nickel
Reagents
Symmetry
Synthesis (chemistry)
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Summary: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-DiP hospheCine, 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.
ISSN:2041-6520
2041-6539
DOI:10.1039/c6sc03614g