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Synlett 2012(1): 49-53  
DOI: 10.1055/s-0031-1289532
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© Georg Thieme Verlag Stuttgart ˙ New York

Gold-Catalyzed Cyclization of Oxo-1,5-enynes

Núria Huguet, Antonio M. Echavarren*
Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona, Spain
Fax: +34(977)920225; e-Mail: aechavarren@iciq.es;
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Publication History

Received 4 August 2011
Publication Date:
19 October 2011 (online)

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Abstract

Cationic gold(I) complexes catalyze the cycloisomerization of oxo-1,5-enynes to form oxatricyclic derivatives through an intramolecular Prins reaction.

Key words

gold - enynes - alkynes - cycloisomerization

    References and Notes

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10

( E )-4-Methyl-6-(phenylsulfonyl)non-4-en-8-ynal (10a): Yellow solid; mp 52-54 ˚C. ¹H NMR (400 MHz, CDCl3):
δ = 9.73 (t, J = 1.5 Hz, 1 H), 7.97-7.73 (m, 2 H), 7.69-7.60 (m, 1 H), 7.56-7.52 (m, 3 H), 5.08 (ddd, J = 10.3, 2.6, 1.3 Hz, 1 H), 3.95 (td, J = 10.2, 3.8 Hz, 1 H), 2.98 (ddd, J = 16.7, 3.8, 2.8 Hz, 1 H), 2.60 (ddd, J = 16.7, 10.2, 2.7 Hz, 2 H), 2.47 (tm, J = 7.5 Hz, 2 H), 2.32 (t, J = 7.4 Hz, 2 H), 1.94 (t, J = 2.7 Hz, 1 H), 1.32 (d, J = 1.3 Hz, 3 H). ¹³C NMR (CDCl3, 100 MHz): δ = 201.27 (CHO), 144.80 (C), 137.37 (C), 134.02 (C), 129.33 (CH), 129.28 (CH), 129.13 (CH), 116.85 (CH), 71.11 (CH), 63.03 (CH), 41.66 (CH2), 31.8 (CH2), 18.86 (CH2), 16.83 (CH3). IR (thin film): 3244 (CH terminal alkyne), 1712 (C=O) cm-¹. HRMS (ESI): m/z [M + Na]+ calcd for C16H18O3SNa: 313.0874; found: 313.0867. ( E )-5-Methyl-7-(phenylsulfonyl)dec-5-en-9-yn-2-one (10b): Yellow solid; mp 53-55 ˚C. ¹H NMR (400 MHz, CDCl3): δ = 7.84-7.82 (m, 2 H), 7.65 (t, J = 7.4 Hz, 1 H), 7.56-7.52 (m, 2 H), 5.06 (dd, J = 10.3, 1.2 Hz, 1 H), 3.95 (td, J = 10.2, 3.8 Hz, 1 H), 2.99 (ddd, J = 16.7, 3.5, 2.9 Hz, 1 H), 2.61 (ddd, J = 16.7, 10.1, 2.6 Hz, 1 H), 2.48 (dd, J = 8.6, 6.6 Hz, 2 H), 2.27 (t, J = 7.8 Hz, 2 H), 2.15 (s, 3 H), 1.94 (t, J = 2.6 Hz, 1 H), 1.31 (d, J = 1.2 Hz, 3 H). ¹³C NMR (CDCl3, 100 MHz): δ = 207.58 (C), 145.43 (C), 137.36 (C), 133.93 (CH), 129.25 (CH), 129.05 (CH), 116.17 (CH), 79.00 (C), 71.02 (CH), 62.99 (CH), 41.52 (CH2), 33.25 (CH2), 30.05 (CH3), 18.82 (CH2), 16.86 (CH3). IR (thin film): 3295 (CH terminal alkyne), 1704 (C=O) cm-¹. HRMS (ESI): m/z [M + Na]+ calcd for C17H20O3SNa: 327.1031; found: 327.1030

11

General procedure for the cyclization of oxo-1,5-enynes : 1,5-Oxoenyne and the gold(I) complex A-G (2-5 mol%) were dissolved in CH2Cl2 (0.5-1.2 mL) and stirred at room temperature until full conversion was observed (reaction monitored by TLC). One drop of Et3N was added and the crude reaction was filtered through Celite and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography on silica gel to provide the cyclized product. (1 S ,3a S ,4 S ,7 R ,7a R )-7-Methyl-1-[(phenylperoxy)thio]-3a,4,5,6,7,7a-hexahydro-1 H -4,7-epoxyindene (11a): ¹H NMR (500 MHz, CDCl3): δ = 7.89-7.85 (m, 2 H), 7.75-7.62 (m, 1 H), 7.61-7.51 (m, 2 H), 5.99 (dt, J = 5.7, 2.0 Hz, 1 H), 5.77 (dt, J = 4.3, 1.9 Hz, 1 H), 4.48 (t, J = 5.6 Hz, 1 H), 4.00-3.98 (m, 1 H), 3.34-3.01 (m, 1 H), 2.74 (dt, J = 9.5, 2.0 Hz, 1 H), 1.73-1.51 (m, 1 H), 1.51-1.33 (m, 2 H), 1.27-1.25 (m, 1 H), 1.21 (s, 3 H). ¹³C NMR (CDCl3, 125 MHz): δ = 141.36 (CH), 136.91 (C), 133.97 (CH), 129.49 (CH), 129.12 (CH), 125.04 (CH), 86.01 (C), 79.03 (CH), 72.35 (CH), 56.03 (CH), 52.88 (CH), 30.32 (CH2), 28.58 (CH2), 20.18 (CH3). HRMS (ESI): m/z [M + Na]+ calcd for C16H18O3SNa: 313.0874; found: 313.0869. (1 S ,3a S ,4 R ,7 S ,7a R )-7-Methyl-1-[(phenylperoxy)thio]-3a,4,5,6,7,7a-hexahydro-1 H -4,7-epoxyindene (11a′): ¹H NMR (500 MHz, CDCl3): δ = 7.88-7.85 (m, 2 H), 7.73-7.60 (m, 1 H), 7.63-7.49 (m, 2 H), 5.92 (dt, J = 5.7, 2.2 Hz, 1 H), 5.62 (dt, J = 5.7, 2.1 Hz, 1 H), 4.26-4.18 (m, 1 H), 4.14 (d, J = 5.1 Hz, 1 H), 2.96 (ddd, J = 7.0, 4.6, 2.3 Hz, 1 H), 2.72 (dd, J = 7.2, 3.1 Hz, 1 H), 1.82-1.74 (m, 1 H), 1.62-1.58 (m, 1 H), 1.56-1.48 (m, 2 H), 1.32 (s, 3 H). ¹³C NMR (CDCl3, 125 MHz): δ = 139.30 (CH), 137.71 (C), 133.90 (CH), 129.23 (CH), 129.17 (CH), 126.02 (CH), 84.58 (C), 78.97 (CH), 74.25 (CH), 58.21 (CH), 50.34 (CH), 36.31 (CH2), 30.75 (CH2), 17.99 (CH3). HRMS (ESI): m/z [M + Na]+ calcd for C16H18O3SNa: 313.0874; found: 313.0882