Synlett 2014; 25(11): 1539-1541
DOI: 10.1055/s-0034-1378348
cluster
© Georg Thieme Verlag Stuttgart · New York

Polyfluorinated Cyclopentadienones as Lewis Acids

Blanca Inés
Max-Planck-Institut für Kohlenforschung, Kaiser Wilhelm Platz 1, 45470 Mülheim an der Ruhr, Germany   Fax: +49(208)3062428   Email: alcarazo@mpi-muelheim.mpg.de
,
Sigrid Holle
Max-Planck-Institut für Kohlenforschung, Kaiser Wilhelm Platz 1, 45470 Mülheim an der Ruhr, Germany   Fax: +49(208)3062428   Email: alcarazo@mpi-muelheim.mpg.de
,
Dominique A. Bock
Max-Planck-Institut für Kohlenforschung, Kaiser Wilhelm Platz 1, 45470 Mülheim an der Ruhr, Germany   Fax: +49(208)3062428   Email: alcarazo@mpi-muelheim.mpg.de
,
Manuel Alcarazo*
Max-Planck-Institut für Kohlenforschung, Kaiser Wilhelm Platz 1, 45470 Mülheim an der Ruhr, Germany   Fax: +49(208)3062428   Email: alcarazo@mpi-muelheim.mpg.de
› Author Affiliations
Further Information

Publication History

Received: 29 April 2014

Accepted after revision: 03 June 2014

Publication Date:
11 June 2014 (online)


Abstract

The ability of 2,3,4,5-tetrakis(trifluoromethyl)cyclopenta-2,4-dien-1-one and 2,3,4,5-tetrakis(pentafluorophenyl)cyclopenta-2,4-dien-1-one to act as organic Lewis acids in the field of frustrated Lewis pair (FLP) chemistry was evaluated. Whereas the former ketone formed zwitterionic adducts with all phosphines studied, the latter did not react with bulky phosphines and, instead, gave completely organic FLPs. Unfortunately, these did not activate dihydrogen, even under high pressures.

Supporting Information

 
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  • 16 In a typical reaction, the appropriate phosphine was added in one portion to a solution of ketone 9 in toluene at r.t., and the resulting slurry was stirred at r.t. overnight. The solvent was then removed under vacuum and the crude product washed with pentane. 12: yellow solid; yield: 66 mg (86%); mp 235 °C (decomp.); IR (neat): 742, 856, 926, 991, 1053, 1093, 1104, 1347, 1402, 1494, 1504, 1523, 1978 cm–1; 1H NMR (400 MHz, CD2Cl2): δ = 1.40 (d, J = 14.7 Hz, 27 H); 13C NMR (151 MHz, CD2Cl2): δ = 29.2, 42.1 (d, J = 33.9 Hz), 77.9, 96.1, 104.2, 113.6 (m), 114.0 (m), 137.2 (dm, J = 250.4 Hz), 137.9 (dm, J = 251.8 Hz), 139.6 (dm, J = 249.0 Hz), 139.9 (dm, J = 249.0 Hz), 144.7 (dm, J = 246.2 Hz), 145.5 (dm, J = 243.4 Hz); 31P NMR (162 MHz, CD2Cl2): δ = 106.7; 19F NMR (282 MHz, CDCl3): δ = –(165.21–165.02) (m, 4 F), –(164.00–163.80) (m, 4 F), –(158.86–158.52) (m, 4 F), –(140.25–140.14) (m, 4 F), –(139.00–138.85) (m, 4 F); HRMS: m/z [M + Na]+ calcd for C41H27OF20PNa: 969.137244; found: 969.137923. 14: yellow solid; yield: 50 mg (93%); mp 229 °C (decomp.); IR (neat): 790, 852, 864, 894, 924, 969, 991, 1060, 1094, 1106, 1287, 1358, 1403, 1475, 1490, 1501, 1522, 1535, 2862, 2933; 1H NMR (400 MHz, CD2Cl2): δ = 0.83–1.00 (m, 4 H), 1.07–1.27 (m, 6 H), 1.38–1.72 (m, 10 H), 2.01–2.12 (m, 2 H), 7.26–7.29 (m, 1 H), 7.32–7.38 (m, 3 H), 7.44–7.48 (m, 1 H), 7.55–7.57 (m, 3 H), 7.70–7.74 (m, 1 H); 13C NMR (101 MHz, CD2Cl2) (partial): δ = 25.7 (d, J = 1.4 Hz), 26.3 (d, J = 3.8 Hz), 26.9 (d, J = 13.3 Hz), 37.2 (d, J = 51.9 Hz), 83.2, 95.5, 103.5, 113.0, 114.0, 127.7 (d, J = 11.4 Hz), 129.2, 129.7, 130.3, 131.9 (d, J = 10.0 Hz), 134.6 (d, J = 14.3 Hz), 134.7, 137.5 (dm, J = 242.7 Hz), 137.9 (dm, J = 247.0 Hz), 139.5 (d, J = 2.4 Hz), 144.7 (dm, J = 242.7 Hz), 145.5 (dm, J = 240.3 Hz), 148.5 (d, J = 8.6 Hz); 31P NMR (162 MHz, CD2Cl2): δ = 80.5; 19F NMR (282 MHz, CDCl3): δ = –(165.21–165.09) (m, 4 F), –(163.99–163.84) (m, 4 F), –159.68 (t, J = 21.1 Hz, 2 F), –159.36 (t, J = 21.0 Hz, 2 F), –(140.52–140.34) (m, 4 F), –139.77 (dt, J = 25.0, 8.7 Hz, 4 F); HRMS: m/z [M + Na]+ calcd for C53H31OF20PNa: 1117.168543; found: 1117.169092.