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

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