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Synlett 2008(11): 1635-1638  
DOI: 10.1055/s-2008-1078490
LETTER
© Georg Thieme Verlag Stuttgart · New York

Zeolite NaY-Promoted Tandem 1,5-Diene-Carbonyl-Ene Dicyclization of α-Geranyl-Substituted Carbonyl Compounds

Christina Efe, Constantinos Tsangarakis, Ioannis N. Lykakis, Christos Raptis, Manolis Stratakis*
Department of Chemistry, University of Crete, Voutes 71003, Iraklion, Greece
Fax: +30(2810)545001; e-Mail: stratakis@chemistry.uoc.gr;
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Publication History

Received 24 March 2008
Publication Date:
11 June 2008 (online)

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Abstract

The mildly acidic zeolite NaY promotes a tandem dicyclization to a variety of α-geranyl-substituted carbonyl compounds to afford 1,2,3,4,4a,5,6,7-octahydronaphthalen-2-ols in moderate to good yields. In certain cases, the diastereoselection is remarkable. The dicyclization occurs by a 1,5-diene cyclization on the geranyl moiety to form selectively γ-cyclogeranyl-substituted carbonyl compounds, which further cyclize through an intermolecular carbonyl-ene reaction.

Key words

zeolites - tandem reactions - cyclizations - diastereo­selectivity

9

Spectroscopic Data of the Intrazeolite ProductsCompound 6a: 1H NMR (300 MHz, CDCl3): δ = 5.44 (br s, 1 H), 2.14 (br d, J = 13.0 Hz, 1 H), 2.08 (d, J = 13.0 Hz, 1 H), 1.97 (m, 2 H), 1.40-1.60 (m, 4 H), 1.31 (m, 1 H), 1.21 (m, 1 H), 1.17 (s, 3 H), 0.89 (s, 3 H), 0.89 (d, J = 6.0 Hz, 3 H), 0.83 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 137.3, 122.0, 71.6, 50.8, 47.6, 40.8, 33.8, 33.6, 31.1, 28.1, 26.7, 25.7, 22.8, 15.2. MS (EI): m/z (%) = 208 (0.2) [M+] , 190, 175, 137 (100), 119, 109, 105, 91, 85, 79.
Compound 6b: 1H NMR (300 MHz, CDCl3): δ = 5.45 (br s, 1 H), 2.35 (br d, J = 13.0 Hz, 1 H), 1.97 (m, 3 H), 1.91 (d, J = 13.0 Hz, 1 H), 1.72 (m, 1 H), 1.62 (m, 1 H), 1.45 (m, 1 H), 1.34 (m, 1 H), 1.22 (m, 1 H), 1.17 (s, 3 H), 1.03 (d, J = 6.0 Hz, 3 H), 0.91 (s, 3 H), 0.83 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 133.2, 122.1, 73.2, 44.6, 40.8, 39.8, 34.0, 31.6, 30.9, 28.3, 27.0, 22.7, 16.6, 14.1. MS (EI): m/z (%) = 208 (0.3) [M+], 190, 175, 134, 119 (100), 105, 91, 79.
Compound 7a: 1H NMR (300 MHz, CDCl3): δ = 5.44 (br s, 1 H), 1.95-2.08 (m, 4 H), 1.15-1.72 (m, 13 H), 0.90 (s, 3 H), 0.84 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 137.1, 122.4, 70.5, 50.4, 47.7, 44.3, 38.6, 33.8, 31.9, 31.1, 28.6, 28.2, 26.2, 25.5, 22.8, 21.7. MS (EI): m/z (%) = 234 (10) [M+], 216, 199, 160, 145, 137, 121, 105, 91 (100), 79.
Compound 8a: 1H NMR (300 MHz, CDCl3): δ = 5.44 (br s, 1 H), 2.29 (br d, J = 13.0 Hz, 1 H), 1.94-2.02 (m, 3 H), 1.58-1.77 (m, 8 H), 1.12-1.44 (m, 3 H), 0.89 (s, 3 H), 0.82 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 137.7, 121.0, 80.0, 45.4, 44.5, 41.6, 38.2, 33.0, 30.9, 27.9, 27.6, 27.5, 25.8, 22.8, 19.8. MS (EI): m/z (%) = 201 (12) [M+], 187, 179, 161, 146, 131 (100), 117, 105, 91, 79.
Compound 9a: 1H NMR (300 MHz, CDCl3): δ = 5.45 (br s, 1 H), 4.03 (m, 1 H), 2.25 (dd, J 1 = 12.5 Hz, J 2 = 2.5 Hz, 2 H), 1.99 (m, 2 H), 1.88 (m, 1 H), 1.67-1.53 (m, 5 H), 1.38 (m, 2 H), 1.20 (m, 1 H), 0.92 (s, 3 H), 0.86 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 135.9, 122.2, 67.3, 47.8, 43.8, 33.6, 33.1, 31.3, 28.0, 25.6, 23.4, 22.8. MS (EI): m/z (%) = 180 (17) [M+], 162, 147, 136, 124, 119, 106 (100), 91, 79,78.
Compound 9b: 1H NMR (300 MHz, CDCl3): δ (selected chemical shifts) = 5.45 (br s, 1 H), 3.85 (m, 1 H) 1.95 (m, 2 H), 1.77 (m, 2 H), 0.98 (s, 3 H), 0.91 (s, 3 H). MS (EI): m/z (%) = 180 (12) [M+], 162, 147, 136 (100), 119, 106, 93, 91, 79, 69.
Compound 10a: 1H NMR (300 MHz, CDCl3): δ = 2.37 (dd, J 1 = 3.5 Hz, J 2 = 16.0 Hz, 1 H), 2.23 (s, 3 H), 2.17 (s, 3 H), 2.03 (t, J = 16.0 Hz, 1 H), 1.89 (dd, J 1 = 3.5 Hz, J 2 = 16.0 Hz, 1 H), 1.63 (m, 1 H), 1.51-1.39 (m, 4 H), 1.26 (m, 1 H), 1.15 (s, 3 H), 0.98 (s, 3 H), 0.87 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 198.8, 162.9, 109.8, 78.4, 47.8, 41.4, 39.5, 33.3, 32.1, 29.8, 21.5, 21.4, 20.6, 19.6, 19.5. MS (EI): m/z (%) = 236 (49) [M+], 218, 203, 193, 175, 161, 151, 137, 123, 113, 109 (100), 91, 81, 69.
Compound 11a: 1H NMR (300 MHz, CDCl3): δ = 5.45 (br s, 1 H), 3.75 (s, 1 H), 2.36 (br d, J = 13.0 Hz, 1 H), 2.22 (s, 3 H), 2.08 (m, 1 H), 2.02 (d, J = 14.5 Hz, 1 H), 1.91 (br d, J = 15.5 Hz, 1 H), 1.86 (dd, J 1 = 7.8 Hz, J 2 = 13.0 Hz, 2 H), 1.50 (dd, J 1 = 3.5 Hz, J 2 = 11.5 Hz, 1 H), 1.37 (m, 1 H), 1.32 (s, 3 H), 1.31 (m, 1 H), 1.17 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 216.7, 135.1, 122.1, 73.9, 54.2, 45.7, 41.7, 36.0, 33.2, 31.2, 28.9, 27.9, 25.1, 23.2, 22.5, 19.4. MS (EI): m/z (%) = 250 (1) [M+], 232, 217, 189 (100), 166, 151, 133, 119, 108, 91, 85, 69.
Compound 11b: 1H NMR (300 MHz, CDCl3): δ = 5.46 (br s, 1 H), 3.75 (s, 1 H), 2.99 (br d, J = 14.1 Hz, 1 H), 2.15 (s, 3 H), 1.98 (m, 2 H), 1.92 (d, J = 14.0 Hz, 1 H), 1.77 (br, 1 H), 1.51 (br d, J = 13.0 Hz, 1 H), 1.43 (d, J = 12.8 Hz, 1 H), 1.30 (m, 1 H), 1.26 (s, 3 H), 1.25 (s, 3 H), 1.22 (m, 1 H). 13C NMR (75 MHz, CDCl3): δ = 212.6, 136.5, 123.1, 72.5, 55.8, 46.7, 44.1, 35.6, 34.1, 31.0, 28.2, 26.7, 24.7, 23.8, 22.6, 19.7. MS (EI): m/z (%) = 250 (1) [M+], 232, 217, 189 (100), 163, 147, 133, 119, 108, 91, 85, 69.
Compound 12a: 1H NMR (300 MHz, CDCl3): δ = 5.49 (br s, 1 H), 4.19 (dq, J 1 = 12.0 Hz, J 2 = 7.0 Hz, 1 H), 4.10 (dq, J 1 = 12.0 Hz, J 2 = 7.0 Hz, 1 H), 2.86 (br d, J = 13.0 Hz, 1 H), 1.89-2.02 (m, 5 H), 1.33 (s, 3 H), 1.26 (t, J = 7.0 Hz, 3 H), 1.24 (s, 3 H), 1.18-1.35 (m, 4 H), 0.91 (s, 3 H), 0.83 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 176.0, 136.5, 123.2, 72.3, 60.1, 50.9, 47.2, 44.0, 36.1, 34.2, 31.0, 28.3, 24.7, 24.2, 22.7, 20.4, 14.3. MS (EI): m/z (%) = 280 (1) [M+], 262, 247, 235, 201, 189 (100), 173, 161, 147, 133, 119, 107, 91, 79, 69.
Compound 13a: 1H NMR (300 MHz, CDCl3): δ = 5.48 (br s, 1 H), 4.24 (dq, J 1 = 12.0 Hz, J 2 = 7.0 Hz, 1 H), 4.10 (dq, J 1 = 12.0 Hz, J 2 = 7.0 Hz, 1 H), 3.02 (br d, J = 13.0 Hz, 1 H), 2.21 (dt, J 1 = 13.0 Hz, J 2 = 7.0 Hz, 1 H), 1.20-2.05 (m, 15 H), 1.26 (t, J = 7.0 Hz, 3 H), 0.89 (s, 3 H), 0.82 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 175.5, 136.4, 123.6, 71.3, 59.9, 52.5, 46.1, 44.6, 34.6, 33.8, 32.1, 31.6, 31.1, 29.7, 28.4, 24.8, 22.8, 21.3, 14.4. MS (EI): m/z (%) = 306 (1) [M+], 288, 260, 245, 232, 215, 199, 189, 176, 159, 145 (100), 131, 117, 105, 91, 79, 67.

12

We observed that the extremely dry zeolite NaY (130 °C for 12 h, and carefully adjusted vacuum at 1.33·10-4 mbar) is much more active, and can promote the cyclization of geranylacetone (1) to α-ambrinol (3) in up to 80% isolated yield within 3 h, with formation of 2b in trace amounts. In our previous publication [2a] we had used extended reaction times to achieve such product selectivity.