Twofold Pauson-Khand Reaction of Cyclic Diynes in Supercritical Ethylene

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.

alkynes - ketones - cyclopentadienes - cobalt - supercritical solvents

References

1a Khand IU. Knox GR. Pauson PL. Watts WE. J. Chem. Soc., Chem. Commun.  1971,  36 

1b Khand IU. Knox GR. Pauson PL. Watts WE. J. Chem. Soc., Perkin Trans. 1  1973,  975 

Reviews:

2a Pauson PL. Tetrahedron  1985,  41:  5855 

2b Pauson PL. Organometallics, In Organic Synthesis   de Meijere A. Dieck HT. Springer; Berlin: 1988.  p.233 

2c Schore NE. In Comprehensive Organic Synthesis   Vol. 5:  Trost BM. Pergamon; Oxford: 1991.  p.1037 

2d Schore NE. Org. React.  1991,  40:  1 

2e Schore NE. In Comprehensive Organometallic Chemistry II   Vol. 12:  Abel EW. Stone FGA. Wilkinson G. Pergamon; Oxford: 1995.  p.703 

2f Geis O. Schmalz HG. Angew. Chem. Int. Ed.  1998,  37:  911 

2g Chung YK. Coord. Chem. Rev.  1999,  188:  297 

2h Brummond KM. Kent JL. Tetrahedron  2000,  56:  3263 

2i Fletcher AJ. Christie SDR. J. Chem. Soc., Perkin Trans. 1  2000,  1657 

3a de Bruin TJM. Milet A. Robert F. Gimbert Y. Greene AE. J. Am. Chem. Soc.  2001,  123:  7184 

3b Yamanaka M. Nakamura E. J. Am. Chem. Soc.  2001,  123:  1703 

4a Donkervoort JG. Gordon AR. Johnstone C. Kerr WJ. Lange U. Tetrahedron  1996,  52:  7391 

4b Rausch BJ. Gleiter R. Tetrahedron Lett.  2001,  42:  1651 

5 Jeong N. Hwang SH. Angew. Chem. Int. Ed.  2000,  39:  636 

6a Kerr WJ. McLaughlin M. Pauson PL. Robertson SM. Chem. Commun.  1999,  21:  2171 

6b Kerr WJ. McLaughlin M. Pauson PL. Robertson SM. J Organomet. Chem.  2001,  630:  104 

6c Kerr WJ. McLaughlin M. Pauson PL. J. Organomet. Chem.  2001,  630:  118 

7 Gleiter R. Merger M. Angew. Chem., Int. Ed. Engl.  1997,  36:  2426 

8 Roers R. Rominger F. Nuber B. Gleiter R. Organometallics  2000,  19:  1578 

9 Brintzinger HH. Fischer R. Mülhaupt R. Rieger B. Waymouth RM. Angew. Chem., Int. Ed. Engl.  1990,  29:  1413 

10 Gleiter R. Merger R. Treptow B. Wittwer W. Pflaesterer G. Synthesis  1993,  6:  558 

11 Gleiter R. Ramming M. Weigl H. Wolfart V. Irngartinger H. Oeser T. Liebigs Ann. Recl.  1997,  1545 

12 Chung YK. Lee BY. Jeong N. Hudecek M. Pauson PL. Organometallics  1993,  12:  220 

13 Dale J. Hubert AJ. King GSD. J. Chem. Soc.  1963,  73 

14 Nicolaou KC. Zuccarello G. Riemer C. Estevez VA. Dai W.-M. J. Am. Chem. Soc.  1992,  114:  7360 

15 Gleiter R. Rittinger S. Langer H. Chem. Ber.  1991,  124:  357 

16 Gleiter R. Rittinger S. Tetrahedron Lett.  1988,  29:  4529 

Reviews:

17a Oakes RS. Clifford AA. Rayner CM. J. Chem. Soc., Perkin Trans. 1  2001,  917 

17b Darr JA. Poliakoff M. Chem. Rev.  1999,  99:  495 

18

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]

19

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.

20

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, R_w(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, R_w(F²) 0.088; (Δρ)max/(Δρ)min: 0.24/-0.24 eÅ^-3.

21

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.

22

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.

23

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.

24

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.

25

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