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. 2017 Feb 1;8(2):1463-1468.
doi: 10.1039/c6sc03614g. Epub 2016 Oct 11.

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

Ioana Knopf  1 , Daniel Tofan  1 , Dirk Beetstra  2 , Abdulaziz Al-Nezari  2 , Khalid Al-Bahily  2 , Christopher C Cummins  1
Affiliations

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

Ioana Knopf et al. Chem Sci. .

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 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.

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Figures

Fig. 1
Fig. 1. Synthetic routes to phosphino-phosphonium salts 2–4, dichloride 11, and macrocyclic diphosphines 5–10 and 12.
Fig. 2
Fig. 2. Solid-state structure of [Me-P2(dmb)2]I (2) with ellipsoids at the 50% probability level and disordered THF omitted for clarity. Representative interatomic distances [Å] and angles [°]: P2–C4 1.813(5), P2–C5 1.817(5), P2–C9 1.791(5), P1–P2 2.1862(17); C9–P2–C4 111.7(2), C9–P2–C5 106.9(2), C4–P2–C5 112.0(2), C9–P2–P1 114.01(19).
Fig. 3
Fig. 3. Solid-state structure of Me2-DPC (5) with ellipsoids at the 50% probability level and hydrogen atoms omitted for clarity. Representative interatomic distances [Å] and angles [°]: P1–C1 1.8433(16), P1–C11 1.8583(16), P1–C18 1.8624(16), P2–C2 1.8421(17), P2–C15 1.8617(16), P2–C14 1.8630(16); C1–P1–C11 96.84(7), C1–P1–C18 98.07(7), C11–P1–C18 101.22(7), C2–P2–C15 97.03(8), C2–P2–C14 98.02(7), C15–P2–C14 101.54(7).
Fig. 4
Fig. 4. Solid-state structure of I2·P2(dmb)2 (I2·1) with ellipsoids at the 50% probability level and disordered solvent and iodine omitted for clarity. Representative interatomic distances [Å] and angles [°]: I1–P1 2.4110(5), I1–I2 3.4169(12), P1–P2 2.1913(7); P1–I1–I2 173.21(4).
Fig. 5
Fig. 5. Reaction scheme depicting the equilibrium between the two structural forms of 11 overlayed on the 31P{1H} 2D EXSY spectrum of 11 acquired at 0 °C in CDCl3.
Fig. 6
Fig. 6. Synthesis of (Cy2-DPC)Ni(CH2CH2COO) (13) from 12 via two complementary routes (see ESI for details).
Fig. 7
Fig. 7. Solid-state structure of nickelalactone (Cy2-DPC)Ni(CH2CH2COO) (13) with ellipsoids at the 50% probability level and hydrogen atoms omitted for clarity. Representative interatomic distances [Å] and angles [°]: Ni1–P1 2.2454(15), Ni1–P2 2.1283(15), Ni1–C3 1.982(6), Ni1–O1 1.899(4), O1–C1 1.283(6), O2–C1 1.225(6); O1–Ni1–P1 90.86(12), O1–Ni1–C3 85.3(2), C3–Ni1–P2 92.56(19), P2–Ni1–P1 91.46(5); P1–Ni1–P2–C41–173.1(2), P2–Ni1–P1–C31 175.33(18).
Fig. 8
Fig. 8. Ball and stick models of dcpe (top) and Cy2-DPC (bottom) with hydrogen atoms omitted for clarity, highlighting the differences in steric profiles between these two diphosphines. Both ligands are viewed along the Z axis, defined using SambVca 2.0 as the P–Ni–P angle bisector in their respective nickelalactone complexes.
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References

    1. Hartwig J., Organotransition Metal Chemistry: From Bonding to Catalysis, University Science books, 1st edn, 2010.
    1. Chan T. H., Ong B. S. J. Org. Chem. 1974;39:1748–1752.
    2. Ignat'eva S. N., Balueva A. S., Karasik A. A., Kulikov D. V., Kozlov A. V., Latypov S. K., Lönnecke P., Hey-Hawkins E., Sinyashin O. G. Russ. Chem. Bull. 2007;56:1828–1837.
    3. Horner L., Walach P., Kunz H. Phosphorus, Sulfur Silicon Relat. Elem. 1978;5:171–184.
    1. Bauer E. B., Ruwwe J., Martin-Alvarez J. M., Peters T. B., Bohling J. C., Hampel F. A., Szafert S., Lis T., Gladysz J. A. Chem. Commun. 2000:2261–2262.
    2. Shima T., Bauer E. B., Hampel F., Gladysz J. A. Dalton Trans. 2004:1012–1028. - PubMed
    1. Alder R. W., Ganter C., Harris C. J., Orpen A. G. J. Chem. Soc., Chem. Commun. 1992:1170–1172.
    1. Alder R. W., Ellis D. D., Hogg J. K., Martín A., Orpen A. G., Taylor P. N. Chem. Commun. 1996:537–538.
    2. Alder R. W., Ganter C., Gil M., Gleiter R., Harris C. J., Harris S. E., Lange H., Orpen A. G., Taylor P. N. J. Chem. Soc., Perkin Trans. 1. 1998:1643–1656.