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Synlett 2014; 25(11): 1539-1541
DOI: 10.1055/s-0034-1378348
DOI: 10.1055/s-0034-1378348
cluster
Polyfluorinated Cyclopentadienones as Lewis Acids
Weitere Informationen
Publikationsverlauf
Received: 29. April 2014
Accepted after revision: 03. Juni 2014
Publikationsdatum:
11. Juni 2014 (online)
![](https://www.thieme-connect.de/media/synlett/201411/lookinside/thumbnails/10.1055-s-0034-1378348-1.jpg)
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
- for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083.
- 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.
For a recent review on the chemistry of frustrated Lewis pairs see:
For metal-free catalyzed hydrogenation see:
It has been demonstrated that the primary attack takes place at the carbon at the position α to the carbonyl group, but even at low temperatures this intermediate rearranges to the thermodynamically more stable 2, See:
A new procedure has been recently reported, see: