A family of cis-macrocyclic diphosphines: modular, stereoselective synthesis and application in catalytic CO2/ethylene couplingElectronic supplementary information (ESI) available: Full experimental, crystallographic and spectroscopic data. CCDC 1477899-1477902. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc03614g
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 2 (dmb) 2 , produced phosphino-phosphon...
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Format | Journal Article |
Language | English |
Published |
30.01.2017
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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
2
(dmb)
2
, produced phosphino-phosphonium salts [R-P
2
(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 Cy
2
-DPC was synthesized in 74% yield from the dichlorodiphosphine Cl
2
P
2
(dmb)
2
. As a first application, these
cis
-macrocyclic diphosphines were used as ligands in the nickel-catalyzed synthesis of acrylate from CO
2
and ethylene, for which they showed promising catalytic activity.
The stereoselective synthesis of a family of
cis
-macrocyclic diphosphines was achieved in only three steps from white phosphorus and commercial materials. These new ligands showed activity in the nickel-catalyzed coupling of CO
2
and ethylene. |
---|---|
AbstractList | 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
2
(dmb)
2
, produced phosphino-phosphonium salts [R-P
2
(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 Cy
2
-DPC was synthesized in 74% yield from the dichlorodiphosphine Cl
2
P
2
(dmb)
2
. As a first application, these
cis
-macrocyclic diphosphines were used as ligands in the nickel-catalyzed synthesis of acrylate from CO
2
and ethylene, for which they showed promising catalytic activity.
The stereoselective synthesis of a family of
cis
-macrocyclic diphosphines was achieved in only three steps from white phosphorus and commercial materials. These new ligands showed activity in the nickel-catalyzed coupling of CO
2
and ethylene. |
Author | Tofan, Daniel Beetstra, Dirk Al-Nezari, Abdulaziz Cummins, Christopher C Al-Bahily, Khalid Knopf, Ioana |
AuthorAffiliation | Department of Chemistry Massachusetts Institute of Technology Fundamental Catalysis SABIC CRD |
AuthorAffiliation_xml | – name: SABIC CRD – name: Department of Chemistry – name: Fundamental Catalysis – name: Massachusetts Institute of Technology |
Author_xml | – sequence: 1 givenname: Ioana surname: Knopf fullname: Knopf, Ioana – sequence: 2 givenname: Daniel surname: Tofan fullname: Tofan, Daniel – sequence: 3 givenname: Dirk surname: Beetstra fullname: Beetstra, Dirk – sequence: 4 givenname: Abdulaziz surname: Al-Nezari fullname: Al-Nezari, Abdulaziz – sequence: 5 givenname: Khalid surname: Al-Bahily fullname: Al-Bahily, Khalid – sequence: 6 givenname: Christopher C surname: Cummins fullname: Cummins, Christopher C |
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DOI | 10.1039/c6sc03614g |
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Notes | For ESI and crystallographic data in CIF or other electronic format see DOI 10.1039/c6sc03614g 1477899-1477902 Electronic supplementary information (ESI) available: Full experimental, crystallographic and spectroscopic data. CCDC |
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Title | A family of cis-macrocyclic diphosphines: modular, stereoselective synthesis and application in catalytic CO2/ethylene couplingElectronic supplementary information (ESI) available: Full experimental, crystallographic and spectroscopic data. CCDC 1477899-1477902. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc03614g |
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