Conclusiones

Unless otherwise noted, all commercially available reagents were used without further purification. Anhydrous DCM was passed through a column on alumina.41 Column

100

chromatography was performed on SilaFlash P60 40-63 μm (230-400 mesh). TLC was

performed on SiliCycle Silica Gel 60 F254 plates and was visualized using either a UV lamp or KMnO4 stain. NMR spectra were recorded on a Bruker Avance 400, 500 or 600 MHz

spectrometer. All deuterated solvents were purchased from Cambridge Isotopes Laboratories, Inc. and stored over activated molecular sieves. The residual solvent protons or carbons were used as internal standards. 1H NMR data are presented as follows: chemical shift in ppm (δ) downfield from tetramethylsilane (multiplicity, coupling constant, integration). The following abbreviations are used in reporting NMR data: s, singlet; d, doublet; t, triplet; q, quartet; dd, doublet of doublets; dt, doublet of triplets; ddd, doublet of doublet of doublets; m, multiplet. Enynes 2.13 and 2.3,11 as well as Ph3PAuNTf242 were synthesized following literature

procedures.

Preparation of starting materials and products Synthesis of the [4.2.0]bicyclo alcohols, 2.11 and 2.12

To a scintillation vial was added enyne (0.41 mmol), nitromethane (2 mL) and water (300 μL). The contents were mixed with vigorous stirring. Ph3PAuNTf2 (0.041 mmol) was added. The

vial was stirred for 2 hours, then concentrated. After crude NMR, the alcohols were purified by silica gel chromatography, with 6:1 hexanes/ethyl acetate as eluent.

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Synthesis of compound 2.11.

The product was obtained as a white solid in 92% yield. 1_{H NMR (600 MHz, CDCl}

3) δ 7.55 – 7.43 (m, 2H), 7.36 – 7.29 (m, 2H), 7.26 – 7.24 (m, 1H), 6.21 – 6.16 (m, 1H), 2.56 – 2.44 (m, 2H), 2.28 (tddd, J = 24.3, 11.6, 5.9, 2.7 Hz, 2H), 1.73 (s (br), 1H), 1.67 (dt, J = 11.0, 9.2 Hz, 1H), 1.52 (dddd, J = 13.7, 6.2, 2.8, 0.8 Hz, 1H), 1.50 – 1.32 (m, 2H), 1.29 (s, 3H). 13_{C NMR} (151 MHz, CDCl3) δ = 140.8, 139.5, 128.2, 127.9, 127.7, 127.0, 72.9, 44.4, 36.4, 29.2, 23.2, 23.0, 22.3. Synthesis of compound 2.12.

The product was obtained as a clear colorless oil in 85% yield. 1_{H NMR (600 MHz,} CDCl3) δ 6.60 (d, J = 2.3 Hz, 2H), 6.38 (t, J = 2.3 Hz, 1H), 6.18 – 6.14 (m, 1H), 3.79 (s, 6H),

2.55 – 2.39 (m, 2H), 2.35 – 2.18 (m, 2H), 1.83 (s (br), 1H), 1.66 (dt, J = 11.0, 9.2 Hz, 1H), 1.54 – 1.47 (m, 1H), 1.43 – 1.34 (m, 2H), 1.28 (s, 3H). 13_{C NMR (151 MHz, CDCl}

3) δ = 160.4, 141.8,

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General procedure for the synthesis of ketone and nitrile trapped products 2.13b – 2.13f

To a 1-dram vial was added enyne 2.12 (0.05 mmol) and DCM (0.3 mL). The appropriate ketone or nitrile was added (0.3 mL), and the contents were stirred. TfOH (1 equiv., 0.05 mmol) was added. The reaction was stirred for 16 hours and concentrated. For ketone-incorporated products 2.13b, 2.13c, and 2.13d, the products were purified by silica gel column

chromatography. Nitrile-incorporated products 2.13e and 2.13f were analyzed as is.

Synthesis of 2.13b.

The product was isolated as a clear colorless oil in 81% yield. 1_{H NMR (600 MHz,} CDCl3) δ 6.64 (d, J = 2.5 Hz, 1H), 6.40 (d, J = 2.4 Hz, 1H), 6.23 (t, J = 4.3 Hz, 1H), 3.85 (s, 3H), 3.80 (s, 3H), 2.50 (q, J = 10.3 Hz, 1H), 2.30 (q, J = 6.1 Hz, 2H), 1.77 (ddd, J = 10.7, 8.5, 2.0 Hz, 1H), 1.65 (s, 3H), 1.64 – 1.60 (m, 1H), 1.48 (s, 3H), 1.40 (t, J = 6.9 Hz, 2H), 1.33 (s, 3H), 1.27 (ddd, J = 11.8, 8.7, 2.0 Hz, 1H). 13_{C NMR (151 MHz, CDCl} 3) δ = 158.6, 156.7, 135.9, 134.2, 123.5, 120.1, 100.0, 98.5, 74.4, 70.3, 55.2, 55.1, 42.8, 33.9, 29.6, 28.8, 28.5, 22.6, 22.5, 22.3.

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Synthesis of 2.13c.

Compound 2.13c was obtained as a mixture of 2.5 : 1 mixture of diastereomers in a 70% overall yield. The crude NMR is provided with the NMR spectra. The major diastereomer was separated and analyzed by NMR. 1_{H NMR (600 MHz, CDCl}

3) δ 6.60 (d, J = 2.5 Hz, 1H), 6.36 (d, J = 2.4 Hz, 1H), 6.20 – 6.15 (m, 1H), 3.83 (s, 3H), 3.75 (s, 3H), 2.48 – 2.41 (m, 1H), 2.26 (dt, J = 8.5, 3.9 Hz, 2H), 2.00 (dq, J = 13.4, 7.3 Hz, 1H), 1.73 (ddd, J = 10.7, 8.5, 2.0 Hz, 1H), 1.68 (dt, J = 13.4, 7.3 Hz, 1H), 1.63 – 1.59 (m, 1H), 1.58 (s, 3H), 1.42 – 1.34 (m, 2H), 1.28 (s, 3H), 1.25 (td, J = 9.7, 2.0 Hz, 2H), 0.55 (t, J = 7.3 Hz, 3H). 13_{C NMR (151 MHz, CDCl} 3) δ = 158.6, 156.7, 136.2, 135.6, 121.9, 120.0, 100.0, 98.4, 70.2, 55.2, 55.2, 43.0, 34.2, 34.2, 28.8, 27.8, 22.7, 22.6, 22.4, 8.4. Synthesis of 2.13d.

Compound 2.13d was isolated in 64% yield as a colorless oil. 1_{H NMR (600 MHz,} CDCl3) δ 6.62 (d, J = 2.4 Hz, 1H), 6.37 (d, J = 2.4 Hz, 1H), 6.19 (t, J = 4.3 Hz, 1H), 3.83 (s, 3H),

104 1H), 1.82 – 1.66 (m, 2H), 1.61 (td, J = 10.6, 10.1, 8.4 Hz, 3H), 1.42 – 1.34 (m, 2H), 1.28 (s, 3H), 1.27 – 1.21 (m, 2H). 13_{C NMR (151 MHz, CDCl} 3) δ = 158.7, 156.7, 136.1, 135.2, 121.4, 120.1, 100.0, 98.5, 84.3, 70.5, 55.2, 55.1, 43.0, 41.1, 38.6, 33.1, 28.6, 25.6, 25.1, 22.7, 22.4, 22.4. Synthesis of 2.13e.

The product 2.13e was obtained as a pale yellow oil in 93% yield. The product contains trace impurities due to the sensitivity of the product to column chromatography. 1_{H NMR (600} MHz, CDCl3) δ 6.77 (d, J = 2.2 Hz, 1H), 6.70 (dd, J = 6.2, 2.4 Hz, 1H), 6.45 (d, J = 2.2 Hz, 1H), 3.98 (s, 3H), 3.95 (s, 3H), 2.92 (s, 3H), 2.53 (dtd, J = 19.2, 5.4, 2.8 Hz, 1H), 2.44 (q, J = 10.4 Hz, 1H), 2.40 – 2.29 (m, 1H), 2.04 (ddd, J = 11.5, 8.8, 2.8 Hz, 1H), 1.71 (s, 3H), 1.68 (m, 1H), 1.62 (ddd, J = 14.2, 6.7, 1.8 Hz, 1H), 1.54 (ddd, J = 11.6, 9.9, 2.8 Hz, 1H), 1.37 (ddd, J = 14.1, 11.2, 5.5 Hz, 1H). 13_{C NMR (151 MHz, CDCl} 3) δ = 174.1, 168.2, 163.8, 140.4, 132.8, 130.0, 107.6, 102.5, 98.2, 57.0, 56.3, 56.1, 42.6, 33.1, 28.4, 24.8, 23.2, 23.1, 23.0. Synthesis of 2.13f.

105

The product 2.13f was obtained as a pale yellow oil in 90% yield. The product contains trace impurities due to the sensitivity of the product to column chromatography. 1_{H NMR (600} MHz, CD2Cl2) δ 6.83 (d, J = 2.2 Hz, 1H), 6.75 (dd, J = 6.2, 2.3 Hz, 1H), 6.49 (d, J = 2.2 Hz, 1H), 3.98 (s, 3H), 3.97 (s, 3H), 3.44 (dq, J = 14.9, 7.5 Hz, 1H), 3.21 (dq, J = 14.1, 7.2 Hz, 1H), 2.60 – 2.50 (m, 1H), 2.44 – 2.28 (m, 2H), 2.06 (ddd, J = 11.4, 8.6, 2.6 Hz, 1H), 1.81 – 1.70 (m, 1H), 1.67 (s, 3H), 1.66 – 1.58 (m, 1H), 1.56 – 1.45 (m, 1H), 1.38 (ddd, J = 14.1, 11.3, 5.7 Hz, 1H), 1.25 (t, J = 7.8 Hz, 3H). 13_{C NMR (151 MHz, CD} 2Cl2) δ = 178.5, 168.4, 163.5, 140.8, 132.8, 129.9, 106.6, 103.0, 98.2, 56.6, 56.4, 56.2, 42.3, 33.0, 30.1, 28.2, 23.1, 23.0, 22.7, 12.1.

106

NMR spectra of new compounds

107

108

Figure 2.7. 1_{H and} 13_C{1_{H} NMR of 2.13b in CDCl}

109

110

111

112

113

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