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Synlett 2008(15): 2267-2270  
DOI: 10.1055/s-2008-1078592
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Molecular Complexity from Aromatics - An Efficient Route to 1,8-Dimethyl-5-spirocyclopropanetricyclo[6.3.0.0²,6]undec-10-one: A Potential Intermediate for Synthesis of Ceratopicanol

Vishwakarma Singh*a, Girish Chandraa, Shaikh M. Mobinb
a Department of Chemistry, Indian Institute of Technology Bombay, Mumbai 400 076, India
Fax: +91(22)25723480; e-Mail: vks@chemiitb.ac.in;
b National Single Crystal X-ray Diffraction Facility, Indian Institute of Technology Bombay, Mumbai 400 076, India
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Publication History

Received 14 May 2008
Publication Date:
15 July 2008 (online)

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Abstract

A new stereoselective synthesis of linearly fused triquinane intermediate from a simple aromatic precursor is described. Cycloaddition of cyclohexa-2,4-dienone and photochemical oxa-di-pi-methane rearrangement in a functionalized tri-cycloundecenone are the key features of our methodology.

Key words

cycloaddition - oxa-di-pi-methane rearrangement - triquinanes - Diels-Alder reaction

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10

All compounds gave satisfactory spectral and analytical data.
Analytical Data for Adduct 7
Mp 95-96 ˚C. IR (film): νmax = 1731 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 5.75 (d, J = 6.24 Hz, 1 H), 5.73-5.64 (m, 1 H), 5.49-5.44 (m, 1 H), 3.29-3.22 (m, 2 H), 3.02 (part of an AB pattern, J = 6.00 Hz, 1 H), 2.91 (part of AB pattern, J = 6.00 Hz, 1 H), 2.74 (superimposed ddd, J 1 = 9.75 Hz, J 2 = 4.17 Hz, 1 H), 2.54-2.45 (m, 1 H), 2.03-1.92 (m, 1 H), 1.75 (d, J = 1.56 Hz, 3 H), 1.06 (s, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 206.0, 144.0, 133.0, 129.0, 120.0, 59.3, 51.6, 49.2, 49.1, 44.5, 42.7, 36.5, 20.2, 12.7 ESI-HRMS: m/z calcd for C14H16O2Na: 239.1048 [M + Na]+. Found: 239.1054 [M + Na]+.

12

Analytical Data for Compound 13
Mp 98-99 ˚C. IR (neat): νmax = 1736 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 5.89 (d, J = 6.40 Hz, 1 H), 3.94-3.88 (m, 4 H), 2.97-2.94 (m, 1 H), 2.52 (dd, J 1 = 4.80 Hz, J 2 = 2.40 Hz, 1H), 2.48-2.26 (m, 3 H), 1.96 (ddd, J 1 = 7.78 Hz, J 2 = 5.49 Hz, J 3 = 2.29 Hz, 1 H), 1.88-1.80 (m, 1 H), 1.77 (d, J = 1.37 Hz, 3 H), 1.63 (AB system, J AB = 13.90 Hz, 2 H), 1.11 (s, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 218.9, 145.0, 123.5, 112.6, 64.2, 64.0, 47.8, 44.9, 44.6, 42.7, 42.1, 40.7, 34.3, 21.1, 19.8. ESI-HRMS: m/z calcd for C15H21O3: 249.1491 [M + H]+. Found: 249.1490 [M + H]+.
Crystal Data of 13
C15H20O3, M 248.31, space group, triclinic, P1, a = 7.1576 (7), b = 7.7250 (6), c = 12.0151 (10) Å, α = 94.193 (7), β = 98.967 (7), γ = 99.838 (8)o, U = 643.17 (10)A³, Z = 2, D c  = 1.282 mg/m³, T = 293 (2) K, F(000) = 268, size = 0.35 × 0.30 × 0.30 mm. Reflections/collected/unique 2441/2248 [R(int) = 0.0198], final R indices [I > 2σ(I)] = R 1 = 0.0427, wR 2 = 0.0955, R indices (all data) R 1 = 0.0877, wR 2 = 0.1091. The complete crystal data can be obtained free of charge from The Cambridge Crystallographic data Centre via www.ccdc.cam.ac.uk/data_request/cif under the CCDC number 687727.

13

Analytical Data for Compound 6
IR (neat): νmax = 1726 cm-¹. ¹H NMR (400 MHz, CDCl3):
δ = 5.78 (d, J = 6.41 Hz, 1 H), 2.94 (dd, J 1 = 6.41 Hz, J 2 = 2.44 Hz, 1 H), 2.75-2.60 (m, 1 H), 2.48-2.30 (m, 1 H), 1.92-1.80 (m merged with Me signal, total 5 H), 1.70-1.62 (m, 1 H), 1.50-1.37 (m, 1 H), 1.27-1.20 (m, 2 H), 1.14 (s, 3 H), 0.50-0.38 (m, 2 H), 0.32-0.22 (m, 2 H). ¹³C NMR (75 MHz, CDCl3): δ = 213.4, 147.4, 120.6, 53.7, 51.0, 46.8, 42.7, 41.4, 39.5, 38.9, 23.0, 20.4, 19.9, 14.7, 6.7. ESI-HRMS: m/z calcd for C15H20ONa: 239.1412 [M + Na]+. Found: 239.1416 [M+ + Na]+.

16

Analytical Data for Compound 5
IR (neat): νmax = 1729 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 2.60-2.50 (m, 1 H), 3.38-2.30 (m, 2 H), 2.10-2.03 (m, 1 H), 1.87-1.76 (m, 2 H), 1.72-1.66 (m, 1 H), 1.62 (d, J = 10.08 Hz, 1 H), 1.40 (s, 3 H), 1.30-1.24 (m, 2 H), 1.22 (s, 3 H), 0.56-0.49 (m, 2 H), 0.37-0.29 (m, 2 H). ¹³C NMR (100 MHz, CDCl3): δ = 214.9, 64.5, 56.8, 48.4, 46.3, 45.4, 45.2, 43.1, 43.0, 38.3, 23.26, 20.5, 16.6, 14.1, 9.7. ESI-HRMS: m/z calcd for C15H20ONa: 239.1412 [M + Na]+. Found: 239.1405 [M + Na]+.

18

Analytical Data for Compound 4
IR (neat): νmax = 1743 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 2.85-2.76 (m, 1 H), 2.56 (dd, J 1 = 18.33 Hz, J 2 = 8.78 Hz, 1 H), 2.43-2.27 (m, 2 H), 2.18-2.06 (m, 2 H), 1.93 (dd, J 1 = 13.56 Hz, J 2 = 9.16 Hz, 1 H), 1.79 (dd, J 1 = 12.83 Hz, J 2 = 7.69 Hz, 1 H), 1.65-1.56 (m, 1 H), 1.55-1.47 (m, 2 H), 1.34 (dd, J 1 = 12.09 Hz, J 2 = 9.16 Hz, 1 H), 1.14 (s, 3 H), 1.03 (s, 3 H), 0.54-0.45 (m, 2 H), 0.34-0.28 (m, 2 H). ¹³C NMR (100 MHz, CDCl3): δ = 219.8, 55.4, 54.0, 52.2, 51.7, 49.5, 45.2, 43.4, 42.0, 37.3, 24.6, 23.8, 19.3, 12.7, 9.8. ESI-HRMS: m/z calcd for C15H23O: 219.1749 [M + H]+. Found: 219.1744 [M + H]+.