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Synlett 2002(5): 0723-0726
DOI: 10.1055/s-2002-25348
LETTER
© Georg Thieme Verlag Stuttgart · New York

Twofold Pauson-Khand Reaction of Cyclic Diynes in Supercritical Ethylene

Bernhard J. Rauscha, Heike Beckerb, Rolf Gleiter*a, Frank Romingera
a Organisch-Chemisches Institut , Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Fax: +49(6221)544205; e-Mail: rolf.gleiter@urz.uni-heidelberg.de;
b BASF Aktiengesellschaft, Forschung und Technologie Chemikalien, GCI/C, M 311, 67056 Ludwigshafen, Germany
e-Mail: heike.becker@basf-ag.de;
Further Information

Publication History

Received 22 January 2002
Publication Date:
07 February 2007 (online)

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Abstract

The cyclic diynes 1 and 7-11 were allowed to react in supercritical (sc) ethylene under Pauson-Khand conditions to give the tricyclic diketones 4 and 12-16 in yields between 47% and 15%, respectively. Our investigations reveal that in the case of cyclic diynes the yields of Pauson-Khand reactions in organic solvents can be tripled, by carrying out the syntheses in supercritical ethylene. The geometry of the resulting sulfur substituted diones 14 and 15 was determined by means of X-ray analysis on single crystals. Additionally, the synthesis of the twofold tethered cyclopentadienes 17 and 18 and the bis(tricarbonyl-manganese) complexes 19a and 19b from tricyclic dione 4 is presented.

Key words

alkynes - ketones - cyclopentadienes - cobalt - supercritical solvents

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Representative Procedure: Cyclotetradeca-1,8-diyne 1 (0.5 g, 2.66 mmol), octacarbonyl dicobalt (1.8 g, 5.3 mmol) and DMSO (1.4 mL, 20 mmol) were placed in a high pressure vessel and subsequently pressured with 110 bar ethylene. After stirring at 110 °C for 40 h the gas was released and the crude reaction mixture was suspended in ethyl acetate. Filtration through a pad of celite and column chromatography on silica with a mixture of light petroleum and ether 1:1 yielded the pure solid diketone 4 (47%). [4b]

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Selected spectroscopic data for 12: Colorless solid, mp 119 °C. 1H NMR (500 MHz, CDCl3): δ = 2.48-2.46 (m, 8 H, CH2), 2.34-2.31 (m, 8 H, CH2), 1.60-1.56 (m, 4 H, CH2), 1.49-1.46 (m, 4 H, CH2). 13C NMR (125 MHz, CDCl3): δ = 210.1 (CO), 174.3 (C=C), 139.2 (C=C), 34.3 (CH2), 29.0 (CH2), 28.7 (CH2), 25.3 (CH2), 24.8 (CH2), 20.6 (CH2). IR (KBr): 2933, 2862, 1692, 1634, 1451, 1366 cm-1. HRMS (EI): m/z calcd for [C18H24O2]+: 272.1777; found: 272.1789. Selected spectroscopic data for 13: Colorless solid, mp 208 °C. 1H NMR (300 MHz, CDCl3): δ = 2.48-2.46 (m, 4 H, CH2), 2.43-2.38 (m, 4 H, CH2), 2.37-2.31 (m, 2 H, CH2), 2.26-2.22 (m, 4 H, CH2), 2.11-2.02 (s, 6 H, CH2). 13C NMR (75 MHz, CDCl3): δ = 210.2 (CO), 174.6 (C=C), 139.0 (C=C), 34.4 (CH2), 34.3 (CH2), 28.8 (CH2), 28.4 (CH2), 22.1 (CH2), 21.5 (CH2). IR (KBr): 2927, 1691, 1637, 1443, 1408, 1367 cm-1. HRMS (EI): m/z calcd for [C16H20O2]+: 244.1463; found: 244.1470. Selected spectroscopic data for 14: Light yellow solid, mp 162 °C. 1H NMR (300 MHz, CDCl3): δ = 3.49 (s, 4 H, CH2S), 2.70-2.68 (m, 4 H, CH2), 2.42-2.39 (m, 4 H, CH2), 2.17-2.12 (m, 4 H, CH2), 1.54-1.45 (m, 4 H, CH2), 1.19-1.09 (m, 2 H, CH2). 13C NMR (75 MHz, CDCl3): δ = 209.2 (CO), 167.7 (C=C), 142.3 (C=C), 33.9 (CH2), 31.6 (CH2), 28.0 (CH2), 27.1 (CH2), 25.6 (CH2), 21.3 (CH2). IR (KBr): 2940, 2859, 1698, 1632, 1446, 1405, 1360, 1329, 1302 cm-1. Elem. Analysis: C17H22O2S requires C, 70.30; H, 7.64; S, 11.04. Found: C, 70.03; H, 7.54; S, 10.88. Selected spectroscopic data for 15: Light yellow solid, mp 128 °C. 1H NMR (300 MHz, CDCl3): δ = 3.45 (s, 4 H, CH2S), 2.63 (t, 4 H, CH2), 2.40 (t, 4 H, CH2), 2.19 (s, 4 H, CH2), 1.59 (s, 4 H, CH2). 13C NMR (75 MHz, CDCl3): δ = 209.3 (CO), 168.0 (C=C), 142.3 (C=C), 34.1 (CH2), 31.1 (CH2), 28.4 (CH2), 24.6 (CH2), 22.4 (CH2). IR (KBr): 2957, 2929, 2898, 2851, 1690, 1634, 1443, 1367, 1344, 1319 cm-1. HRMS (EI): m/z calcd for [C16H20O2S]+: 276.1184; found: 276.1181. Selected spectroscopic data for 16: Colorless solid, mp 178 °C. 1H NMR (300 MHz, CDCl3): δ = 3.30-3.23 (m, 4 H, CH2), 2.78-2.70 (m, 4 H, CH2), 2.47-2.44 (m, 4 H, CH2), 2.06 (s, 2 H, CH2), 1.56 (s, 4 H, CH2). 13C NMR (75 MHz, CDCl3): δ = 210.0 (CO), 167.8 (C=C), 141.6 (C=C), 34.7 (CH2), 29.1 (CH2), 27.8 (CH2), 21.7 (CH2), 20.6 (CH2). IR (KBr): 2934, 2906, 2862, 1692, 1636, 1442, 1361, 1328 cm-1. HRMS (EI): m/z calcd for [C15H18O2S]+: 262.1027; found: 262.1018.

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Relevant structural parameters for 14: Crystal size: 0.28 × 0.28 × 0.13 mm3; crystal system: orthorhombic; space group P212121; Z = 4; a = 8.3763(1); b = 10.3518(2); c = 16.0565(1) Å; absorption coefficient µ = 0.228 mm-1; reflections collected/independent/observed: 14437/3185/2706; parameters: 252; goodness-of-fit on F2: 1.00, R (F) 0.031, Rw(F2) 0.064; (Δρ)max/(Δρ)min: 0.13/-0.23 eÅ-3. Relevant structural parameters for 15: crystal size: 0.41 × 0.22 × 0.15 mm3; crystal system: triclinic; space group P1; Z = 2; a = 8.5560(2), b = 9.3278(3), c = 9.4021(3) Å; α = 94.646(1)°, β = 96.352(1)°, γ = 90.626(1)°; absorption coefficient µ = 0.217 mm-1; reflections collected/independent/observed: 7730/3388/2786; parameters: 181; goodness-of-fit on F2: 1.05, R (F) 0.035, Rw(F2) 0.088; (Δρ)max/(Δρ)min: 0.24/-0.24 eÅ-3.

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Selected spectroscopic data for 17: Colorless oil. CI-MS [C22H32]+: 297 [M + H]+; HRMS (EI): m/z calcd for [C22H32]+: 296.2504; found: 296.2523. Selected spectroscopic data for 18: Colorless oil. CI-MS [C32H36]+: 421 [M + H]+; HRMS (EI): m/z calcd for [C32H36]+: 420.2817; found: 420.2816.

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Representative Procedure: Dione (0.03 g 0.1 mmol) 4
was dissolved in tetrahydrofuran (10 mL). At -78 °C phenyllithium (0.14 mL, 0.22 mmol) was added in a dropwise fashion and the reaction mixture was allowed to warm up to r.t. After addition of ammonium chloride (50 mL) the two phases were separated and the aq layer was extracted with ether (3 × 50 mL). The combined organic layers were mixed with 2 M HCl, vigorously stirred for 5 min and neutralized with NaHCO3. After drying (MgSO4) the solvent was removed and the crude product was purified by filtration through a pad of alumina (grade III, neutral, light petroleum) to yield 92% of 18 as colorless oil.

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Cyclopentadiene (17; 40 mg, 0.14 mmol) and decacarbonyl dimanganese (115 mg, 0.3 mmol) were dissolved in xylene (25 mL ) and refluxed at 160 °C for 3 d. After evaporation of the solvent the crude product was purified by column chromatography (silica, light petroleum/ether 75:1) yielding 15% of 19a and 19b as yellow oil.

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Selected spectroscopic data for 19a and 19b(mixture): Yellow oil. 1H NMR (300 MHz, CDCl3): δ = 4.44-4.42 (m, 4 H, CpH), 2.24-2.19 (m, 8 H, CH2), 1.89 (s, 6 H, CH3), 1.58-1.56 (m, 4 H, CH2), 1.38-1.34 (m, 8 H, CH2). 13C NMR (75 MHz, CDCl3): δ = 226.1 (CO), 103.8 (CpC), 102.2 (CpC), 99.2 (CpC), 81.0 (CpC), 79.1 (CpC), 31.1 (CH2), 29.0 (CH2), 27.6 (CH2), 26.2 (CH2), 24.9 (CH2), 12.8 (CH3). IR (KBr): 2932, 2859, 2009, 1912, 1461, 1382 cm-1. HRMS (EI): m/z calcd for [C28H30Mn2O6]+: 572.0804; found: 572.0809.

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Rausch, B. J.; Gleiter, R.; Rominger, F. J. Chem. Soc., Dalton Trans. 2002, in press.