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Synlett 2006(4): 0527-0532  
DOI: 10.1055/s-2006-932466
LETTER
© Georg Thieme Verlag Stuttgart · New York

Selectivity in Cobalt Carbonyl Mediated Cycloaddition of Dienynes

Kang Hyun Park, Soo Young Choi, So Yeon Kim, Young Keun Chung*
Intelligent Textile System Research Center, and Department of Chemistry, College of Natural Sciences, Seoul National University, Seoul 151-747, Korea
Fax: +82(2)8890310; e-Mail: ykchung@snu.ac.kr;
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Publikationsverlauf

Received 25 October 2005
Publikationsdatum:
20. Februar 2006 (online)

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Abstract

Dicobalt octacarbonyl mediated cycloaddition of dienynes in the presence of carbon monoxide has been studied. Three main competing reaction routes, two carbonylative cycloaddition reactions and a Diels-Alder reaction, have been recognized depending upon the substrate and reaction conditions. Judicious design of the substrate and selection of reaction conditions allow control of the reaction pathway.

Key words

cobalt carbonyl - cycloadditions - dienynes - carbon monoxide - Diels-Alder

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Crystal data for 2a: monoclinic, P21/a, a = 11.7068 (14), b = 15.7393 (17), c = 13.9213 (12) Å, β = 90.707 (6)°, limiting indices -11 £ h £ 14, -15 £ k £ 18, -15 £ l £ 17, reflections collected/unique 12136/4429 (R int = 0.2320), final R indices [I > 2σ(I)] R1 = 0.0831, wR2 = 0.1130. For 5h: triclinic, P-1, a = 6.5446 (3), b = 11.3786 (9), c = 13.9632 (13)Å, α = 105.233 (3), β = 99.165 (5), γ = 101.332 (4)°, limiting indices -5 £ h £ 8, -14 £ k £ 11, -15 £ l £ 18, reflections collected/unique 5277/4305 (R int = 0.0246), final R indices [I > 2σ(I)] R1 = 0.0577, wR2 = 0.1240. Crystallographic data for 2a and 5h have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication numbers of CCDC 287305 and 287306, respectively. These data can be obtained free charge via www.ddcd.cam.ac.uk/consts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB21EZ, UK; fax: +44 (1223)336033; or deposit@ddcd.cam.ac.uk].

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General Comments.
Thin-layer chromatography (TLC) was performed on 0.25 mm Merck silica gel coated plates treated with a UV (254 nm) and acidic p-anisaldehyde stain followed by gentle heating. TLC plates were visualized by ultraviolet light and treatment with acidic p-anisaldehyde staining solution. THF was purified by distillation from sodium/benzophenone under nitrogen, toluene was distilled from sodium under nitrogen, CH2Cl2 was distilled form P2O5 under nitrogen. Reagents were purchased from Aldrich Chemical Co. and Strem Chemical Co. and were used as received. All yields are based upon isolated material. 1H NMR and 13C NMR spectra were obtained with a Bruker 300 MHz spectrometer. Coupling constants (J values) are reported in Hertz (Hz), and spin multiplicities are indicated by the following symbols: s(singlet), d(doublet), t(triplet), q(quartet), m(multiplet). Infrared spectra were recorded on a Shimadzu IR-470 spectrometer. IR spectra were obtained as films on NaCl by evaporation of solvent or in CHCl3 solution. Elemental analyses were done at the National Center for Inter-University Research Facilities, Seoul National University. High resolution mass spectra were obtained at Korea Basic Science Institute (Daegu, Korea). High resolution mass spectrometry (HRMS) data are reported in the form of m/z (intensity relative to base peak = 100). Microwave reactions were carried out on a CEM Discover microwave reactor with a circular, single mode, self-tuning microwave applicator operating at 2450 MHz. The reaction vessel was purged with nitrogen prior to the addition of reagents. Flash chromatography was performed using Merck Silica Gel 60 (230-400 mesh). Diffraction data of 2a and 5h for structure determination were measured by an Enraf-Nonius CCD single-crystal X-ray diffractometer at r.t. using graphite-monochromated MoKα radiation (λ = 0.71013 Å). Preliminary orientation matrixes and unit cell parameters were obtained from the peaks of the first 10 frames and then refined using the whole data set. Frames were integrated and corrected for Lorentz and polarization effects using DENZO. The structure was solved by direct methods using SHELXS-97 and refined by full-matrix least squares fitting with SHELXL-97. All non-hydrogen atoms were refined anisotropically, and all hydrogen atoms not involving hydrogen bonding were treated as idealized contributions.
Analytical Data.
6-Phenyl-4-propenyl-3a,4-dihydro-1 H ,3 H -cyclo-penta[ c ]furan-5-one (2a).
1H NMR (CDCl3): δ = 1.77 (d, J = 4.9 Hz, 3 H), 2.96 (m, 1 H), 3.24 (m, 1 H), 3.32 (dd, J = 7.6, 11.0 Hz, 1 H), 4.43 (t, J = 7.4 Hz, 1 H), 4.61 (d, J = 16.5 Hz, 1 H), 4.93 (dd, J = 1.5, 16.5 Hz, 1 H), 5.67 (m, 2 H), 7.36 (m, 3 H), 7.53 (m, 2 H) ppm. 13C NMR (CDCl3): δ = 18.3, 50.4, 56.5, 66.7, 71.4, 126.4, 128.2, 128.8, 128.9, 130.0,130.9, 133.5, 174.6, 206.6 ppm. IR: νCO = 1706 cm-1. HRMS: m/z calcd for C16H16O2: 240.1150; found: 240.1151. Anal. Calcd for C16H16O2: C, 79.96; H, 6.72. Found: C, 80.17; H, 6.88.
6-Butyl-4-propenyl-3a,4-dihydro-1 H ,3 H -cyclo-penta[ c ]furan-5-one (2b).
1H NMR (CDCl3): δ = 0.90 (t, J = 7.2 Hz, 3 H), 1.31 (m, 2 H), 1.43 (m, 2 H), 1.75 (d, J = 5.8 Hz, 3 H), 2.14 (qui, J = 7.4 Hz, 1 H), 2.27 (qui, J = 7.4 Hz, 1 H) 2.74 (m, 1 H), 3.08 (m, 1 H), 3.27 (dd, J = 8.0, 11.1 Hz, 1 H), 4.36 (t, J = 7.8 Hz, 1 H), 4.51 (dd, J = 0.7, 15.7 Hz, 1 H), 4.61 (dd, J = 1.1, 15.7 Hz, 1 H), 5.60 (m, 2 H) ppm. 13C NMR (CDCl3): δ = 14.0, 18.4, 22.8, 24.5, 30.0, 50.4, 55.1, 65.3, 71.8, 126.6, 129.7, 135.7, 173.5, 208.9 ppm. IR: νCO = 1707 cm-1. HRMS: m/z calcd for C14H20O2: 220.1463; found: 220.1467.
6-Phenyl-4-propenyl-2-(toluene-4-sulfonyl)-2,3,3a,4-tetrahydro-1 H -cyclopenta[ c ]pyrrol-5-one (2c).
1H NMR (CDCl3): δ = 1.75 (d, J = 6.0 Hz, 3 H), 2.40 (s, 3 H), 2.66 (dd, J = 9.3, 10.8 Hz, 1 H), 2.86 (m, 1 H), 3.14 (m, 1 H), 4.06 (m, 1 H), 4.13 (d, J = 8.7 Hz, 1 H), 4.65 (dd, J = 1.7, 17.1 Hz, 1 H), 5.60 (m, 2 H), 7.31 (d, J = 8.1 Hz, 2 H), 7.35-7.47 (m, 5 H), 7.72 (d, J = 8.3 Hz, 2 H) ppm. 13C NMR (CDCl3): δ = 14.3, 18.4, 21.7, 22.8, 31.8, 48.6, 48.8, 51.9, 56.9, 125.8, 127.6, 128.3, 128.9, 129.1, 130.1, 130.2, 130.4, 133.6, 134.9, 144.3, 169.3, 205.4 ppm. IR: νCO = 1709 cm-1. HRMS: m/z calcd for C23H23O3NS: 393.1399; found: 393.1400.
4-Propenyl-2-(toluene-4-sulfonyl)-2,3,3a,4-tetrahydro-1 H -cyclopenta[ c ]pyrrol-5-one (2d).
1H NMR (CDCl3): δ = 1.73 (d, J = 7.2 Hz, 3 H), 2.45 (s, 3 H), 2.64-2.72 (m, 2 H), 3.07 (m, 1 H), 3.97-4.10 (m, 2 H), 4.35 (d, J = 16.8 Hz, 1 H), 5.45 (m, 1 H), 5.59 (m, 1 H), 5.98 (s, 1 H), 7.36 (d, J = 8.0 Hz, 2 H), 7.74 (d, J = 8.3 Hz, 2 H) ppm. 13C NMR (CDCl3): δ = 18.4, 21.8, 47.9, 50.5, 52.2, 56.1, 124.9, 125.5, 127.7, 130.2, 130.6, 133.4, 144.4, 176.6, 207.5 ppm. IR: νCO = 1710 cm-1. HRMS: m/z calcd for C17H19O3NS: 317.1086; found: 317.1085.
5-Oxo-6-phenyl-4-propenyl-3,3a,4,5-tetrahydro-1 H -pentalene-2,2-dicarboxylic Acid Diethyl Ester (2e).
1H NMR (CDCl3): δ = 1.07 (t, J = 7.1 Hz, 3 H), 1.15 (t, J = 7.1 Hz, 3 H), 1.60 (d, J = 5.8 Hz, 3 H), 1.70 (t, J = 12.4 Hz, 1 H), 2.69-2.78 (m, 2 H), 2.87 (m, 1 H), 3.16 (d, J = 19.5 Hz, 1 H), 3.50 (d, J = 19.4 Hz, 1 H), 4.01 (m, 2 H), 4.13 (dd, J = 7.0, 14.1 Hz, 2 H), 5.42 (m, 1 H), 5.54 (m, 1 H), 7.12-7.43 (m, 5 H) ppm. 13C NMR (CDCl3): δ = 14.1, 14.2, 18.3, 36.1, 38.4, 50.0, 58.8, 61.3, 61.5, 62.10, 62.13, 63.3, 126.8, 128.3, 128.48, 128.55, 129.6, 131.2, 134.3, 170.8, 171.7, 176.2, 206.8 ppm. IR: νCO = 1723 cm-1. HRMS: m/z calcd for C23H26O5: 382.1780; found: 382.1780.
6-Methyl-5-oxo-4-propenyl-3,3a,4,5-tetrahydro-1 H -pentalene-2,2-dicarboxylic Acid Diethyl Ester (2f).
1H NMR (CDCl3): δ = 1.21 (m, 6 H), 1.65-1.67 (m, 6 H), 1.73 (m, 1 H), 2.64 (m, 1 H), 2.77 (m, 2 H), 3.13 (dd, J = 18.9, 28.1 Hz, 2 H), 4.16 (m, 4 H), 5.41 (m, 1 H), 5.56 (m, 1 H) ppm. 13C NMR (CDCl3): δ = 9.0, 14.2, 18.4, 34.1, 38.8, 49.8, 57.5, 61.1, 62.1, 62.3, 127.1, 129.4, 131.9, 171.2, 175.5, 209.2 ppm. IR: νCO = 1722 cm-1. HRMS: m/z calcd for C18H24O5: 320.1624; found: 320.1621.
5-Oxo-4-propenyl-3,3a,4,5-tetrahydro-1 H -pentalene-2,2-dicarboxylic Acid Diethyl Ester ( 2g).
1H NMR (CDCl3): δ = 1.28 (m, 6 H), 1.74 (d, J = 6.2 Hz, 3 H), 1.84 (t, J = 12.5 Hz, 1 H), 2.78 (m, 1 H), 2.84 (dd, J = 7.8, 12.8 Hz, 1 H), 3.00 (m, 1 H), 3.30 (dd, J = 19.1, 36.9 Hz, 2 H), 4.24 (m, 4 H), 5.48 (m, 1 H), 5.63 (m, 1 H), 5.93 (m, 1 H) ppm. 13C NMR (CDCl3): δ = 14.2, 18.3, 35.3, 38.5, 51.8, 58.4, 61.0, 62.2, 62.3, 124.4, 126.6, 129.8, 170.1, 171.6, 183.3, 209.4 ppm. IR: νCO = 1723 cm-1. HRMS: m/z calcd for C17H22O5: 306.1467; found: 306.1466.
7-Phenyl-2-(toluene-4-sulfonyl)-2,3,3a,6-tetrahydro-1 H -isoindole (3h). 1H NMR (CDCl3): δ = 2.35 (s, 3 H), 2.63 (dd, J = 11.2, 8.8 Hz, 1 H), 2.83-2.88 (m, 1 H), 2.96-2.99 (m, 1 H), 3.05-3.22 (m, 1 H), 3.63 (d, J = 14.0 Hz, 1 H), 3.80 (dd, J = 8.7, 7.7 Hz, 1 H), 4.07-4.14 (m, 1 H), 5.67 (d, J = 10.3 Hz, 1 H), 5.80-5.86 (m, 1 H), 7.05 (d, J = 8.3 Hz, 2 H), 7.19-7.27 (m, 1 H), 7.58 (d, J = 8.3 Hz, 2 H) ppm. HRMS: m/z calculated for C21H21O2SN: 351.1293; found: 351.1296. Anal. Calcd for C21H21O2SN: C, 71.77; H, 6.02; N, 3.99. Found: C, 71.80; H, 5.69; N, 3.45.
7-Butyl-2-(toluene-4-sulfonyl)-2,3,3a,6-tetrahydro-1 H -isoindole (3i). 1H NMR (CDCl3): δ = 0.87 (t, J = 7.1 Hz, 3 H), 1.21-1.31 (m, 4 H), 1.81-2.01 (m, 2 H), 2.42 (s, 3 H), 2.45-2.53 (m, 1 H), 2.57 (dd, J = 11.5, 8.6 Hz, 2 H), 2.93-3.11 (m, 1 H), 3.79-3.84 (m, 2 H), 3.97 (d, J = 13.2 Hz, 1 H), 5.65 (d, J = 9.9 Hz, 2 H), 5.75-5.81 (m, 1 H), 7.31 (d, J = 8.0 Hz, 2 H), 7.72 (d, J = 8.2 Hz, 2 H) ppm. 13C NMR (CDCl3): δ = 14.3, 19.0, 23.2, 29.1, 30.5, 33.5, 49.1, 52.9, 55.5, 127.2, 127.8, 128.7, 128.9, 129.9, 131.1 ppm. HRMS: m/z calcd for C19H25O2SN: 331.1606; found: 331.1601.
2-(Toluene-4-sulfonyl)-2,3,3a,6-tetrahydro-1 H -isoindole (3j). 1H NMR (CDCl3): δ = 2.42 (s, 3 H), 2.62-2.70 (m, 3 H), 2.98 (t, J = 8.3 Hz, 1 H), 3.73 (d, J = 13.1 Hz, 1 H), 3.83 (t, J = 8.3 Hz, 1 H), 3.98-4.04 (m, 1 H), 5.50-5.58 (m, 1 H), 5.62-5.69 (m, 1 H), 5.72-5.83 (m, 1 H), 7.31 (d, J = 8.4 Hz, 2 H), 7.71 (d, J = 8.3 Hz, 2 H) ppm.
( E )-4-Ethylidene-6-phenyl-2-(toluene-4-sulfonyl)-2,3,3a,4-tetrahydro-1 H -cyclopenta[ c ]pyrrol-5-one (5h). 1H NMR (CDCl3): δ = 1.92 (d, J = 7.2 Hz, 3 H), 2.40 (s, 3 H), 2.60 (dd, J = 10.9, 9.0 Hz, 1 H), 3.74 (t, J = 8.6 Hz, 1 H), 4.03 (dd, J = 16.3, 1.5 Hz, 1 H), 4.22 (t, J = 8.6 Hz, 1 H), 4.66 (dd, J = 16.3, 1.7 Hz, 1 H), 6.79 (qd, J = 7.2, 1.9 Hz, 1 H), 7.29 (d, J = 8.2 Hz, 2 H), 7.37-7.45 (m, 3 H), 7.49-7.53 (m, 2 H), 7.70 (d, J = 8.3 Hz, 2 H) ppm. 13C NMR (CDCl3): δ = 15.8, 21.7, 44.8, 48.1, 50.1, 127.5, 128.4, 128.8, 129.1, 130.2, 130.6, 132.9, 133.9, 137.2, 137.7, 144.2, 165.8, 195.3 ppm. IR: νCO = 1699 cm-1. HRMS: m/z calcd for C22H21O3SN: 379.1242; found: 379.1242. Anal. Calcd for C22H21O3SN: C, 69.63; H, 5.58; N, 5.58. Found: C, 69.73; H, 6.02; N, 3.26.
( E )-6-Butyl-4-ethylidene-2-(toluene-4-sulfonyl)-2,3,3a,4-tetrahydro-1 H -cyclopenta[ c ]pyrrol-5-one (5i). 1H NMR (CDCl3): δ = 0.77 (t, J = 7.2 Hz, 3 H), 1.04-1.18 (m, 2 H), 1.21-1.30 (m, 2 H), 1.78 (d, J = 7.1 Hz, 3 H), 1.96-2.05 (m, 1 H), 2.11-2.21 (m, 1 H), 2.36 (s, 3 H), 2.46 (dd, J = 10.9, 9.0 Hz, 1 H), 3.48 (t, J = 9.0 Hz, 1 H), 3.91 (d, J = 15.5 Hz, 1 H), 4.05 (t, J = 8.5 Hz, 1 H), 4.19 (d, J = 15.6 Hz, 1 H), 6.56 (qd, J = 7.13, 1.6 Hz, 1 H), 7.27 (d, J = 8.1 Hz, 2 H), 7.66 (d, J = 8.2 Hz, 2 H) ppm. 13C NMR (CDCl3): δ = 13.9, 15.7, 21.7, 22.6, 24.2, 30.0, 44.5, 46.5, 50.8, 127.6, 130.1, 131.7, 133.6, 136.7, 140.2, 144.2, 164.3, 195.3 ppm. IR: νCO = 1698 cm-1. HRMS: m/z calcd for C20H25O3SN: 359.1555; found: 359.1550.
( Z )-4-Ethylidene-6-phenyl-2-(toluene-4-sulfonyl)-2,3,3a,4-tetrahydro-1 H -cyclopenta[ c ]pyrrol-5-one (6h). 1H NMR (CDCl3): δ = 2.27 (dd, J = 7.4, 1.1 Hz, 3 H), 2.40 (s, 3 H), 2.57 (dd, J = 10.8, 9.0 Hz, 1 H), 3.67 (t, J = 9.9 Hz, 1 H), 4.02 (dd, J = 16.5, 1.5 Hz, 1 H), 4.05 (t, J = 8.6 Hz, 1 H), 4.65 (dd, J = 16.4, 1.7 Hz, 1 H), 6.18 (qd, J = 7.4, 1.4 Hz, 1 H), 7.30 (d, J = 8.2 Hz, 2 H), 7.37-7.44 (m, 3 H), 7.49-7.52 (m, 2 H), 7.70 (d, J = 8.3 Hz, 2 H) ppm. 13C NMR (CDCl3): δ = 14.3, 23.9, 46.8, 48.5, 50.7, 127.6, 128.5, 130.2, 130.7, 131.1, 132.7, 133.9, 135.9, 136.9, 138.9, 144.2, 167.9, 194.8 ppm. IR: νCO = 1694 cm-1. HRMS: m/z calcd for C22H21O3SN: 379.1242; found: 379.1239.
( Z )-6-Butyl-4-ethylidene-2-(toluene-4-sulfonyl)-2,3,3a,4-tetrahydro-1 H -cyclopenta[ c ]pyrrol-5-one (6i). 1H NMR (CDCl3): δ = 0.76-0.81 (m, 3 H), 1.10-1.30 (m, 4 H), 1.44-1.58 (m, 2 H), 2.12 (d, J = 7.4 Hz, 3 H), 2.36 (s, 3 H), 2.44 (dd, J = 10.8, 8.9 Hz, 1 H), 3.40 (t, J = 9.1 Hz, 1 H), 3.86-3.93 (m, 2 H), 4.13-4.17 (m, 1 H), 5.60 (qd, J = 7.4, 1.2 Hz, 1 H), 7.27 (d, J = 8.0 Hz, 2 H), 7.65 (d, J = 8.0 Hz, 2 H) ppm. 13C NMR (CDCl3): δ = 11.1, 13.9, 21.7, 22.7, 24.1, 30.0, 38.9, 46.9, 51.4, 127.6, 130.1, 131.1, 135.2, 135.9, 141.4, 144.2, 163.9 ppm. IR: νCO = 1692 cm-1. HRMS: m/z calcd for C20H25O3SN: 359.1555; found: 359.1553.