A family of cis-macrocyclic diphosphines: modular, stereoselective synthesis and application in catalytic CO{subscript 2]/ethylene coupling
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Author(s)
Beetstra, Dirk
Al-Nezari, Abdulaziz
Al-Bahily, Khalid
Knopf, Ioana
Tofan, Daniel
Cummins, Christopher C
Date Issued
October 2016
Journal
Chemical Science
Publisher
Royal Society of Chemistry
Citation
Knopf, Ioana, et al. “A Family of Cis-Macrocyclic Diphosphines: Modular, Stereoselective Synthesis and Application in Catalytic CO[subscript 2]/Ethylene Coupling.” Chemical Science, vol. 8, no. 2, 2017, pp. 1463–68.
Version
Final published version
Abstract
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 P[subscript 2](dmb)[subscript 2], produced phosphino-phosphonium salts [R-P[subscript 2](dmb)[subscript 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 Cy[subscript 2]-DPC was synthesized in 74% yield from the dichlorodiphosphine Cl[subscript 2]P[subscript 2](dmb)[subscript 2]. As a first application, these cis-macrocyclic diphosphines were used as ligands in the nickel-catalyzed synthesis of acrylate from CO[subscript 2] and ethylene, for which they showed promising catalytic activity.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1039/c6sc03614g
