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1 Supporting Information Dicobaltoctacarbonyl-Mediated Synthesis of Tricyclic 5,6-Diydropyran-2-one derivatives via Tandem Cycloaddition Reaction between cis-epoxyalkynes, Tethered lefin and Carbon Monoxide. Arjan dedra, Shie-Fu Lush and Rai-Shung Liu*, Department of Chemistry, National Tsing-Hua University, Hsinchu, Taiwan, RC and Department of Medicinal Technology, Yuanpei University, Hsinchu, Taiwan, Contents: (1) Representative synthetic procedures for cis-epoxy ene-ynes. Synthesis of cis-epoxyenynes 7, 14 and S1 (2) Spectral data for compounds S5 S1

2 (1) Representative synthetic procedures for cis-epoxy ene-ynes. (A) Synthesis of (2S*,3R*)-3-(allyloxymethyl)-2-methyl-2-(oct-1-ynyl)oxirane (7) Scheme S-1 n-c 6 H 13 Br Na S-7 86% n-c6 H 13 S-8 m-cpba 66% n-c6 H 13 7 Synthesis of (Z)-1-(allyloxy)-3-methylundec-2-en-4-yne (S-8). To a THF (50 ml) suspension of NaH (122 mg, 5.0 mmol) was added allyl alcohol (290 mg, 5.0 mmol) at 0 o C and stirred for 30 min at same temperature before addition of allyl bromide S-7 (1.02 g, 4.2 mmol). The reaction mixture was stirred for 4 h at 23 o C under a N 2 atmosphere. To the solution was added a NH 4 Cl solution, and the organic layer was extracted with diethyl ether and dried over MgS0 4. The concentrated residues were chromatographed through a silica column (hexane-ether, 1:1) to give epoxyalkyne S-8 as a colorless oil (0.80 g, 3.60 mmol, 86.0%). Synthesis of (2S*,3R*)-3-(allyloxymethyl)-2-methyl-2-(oct-1-ynyl)oxirane (7). To a CH 2 Cl 2 solution (20 ml) of compound s-8 (0.50 g, 2.27 mmol) was added m-chloroperbenzoic acid (0.39 g, 2.5 mmol) and the mixtures were stirred for 12 h at 23 0 C before quenching with NaHC 3 solution. The organic layer was extracted with diethyl ether, dried over MgS 4. The resulting solution was filtered through a small Al 2 3 bed, concentrated and eluted through a Et 3 N-pretreated silica column (diethyl ether-hexane, 2:1) to afford the epoxyalkyne 7 as a colourless oil (0.352 mg, 1.49 mmol, 65 %). (B) Synthesis of rel-(s)-1-((2r,3s)-3-methyl-3-(oct-1-ynyl)oxiran-2-yl)but-3-enyl acetate (14). S2

3 Scheme S-2 1) swern oxid. H H n-c 6 H 2) allylmgbr 13 S-9 75% n-c 6 H 13 S-10 m-cpba 85% n-c 6 H 13 H (Ac) 2, Et 3 N 89% Ac S-11 n-c 6 H Synthesis of (Z)-6-methyltetradeca-1,5-dien-7-yn-4-ol (S-10). To a 50 ml two-necked flask was placed 1.22 ml (14.0 mmol) of oxalyl chloride and 10 ml of dry dichloromethane. The solution was cooled to 60 ºC to 70 ºC and a CH 2 Cl 2 (20 ml) of DMS (2.0 ml, 28.0 mmol) was added. After 20 min, a CH 2 Cl 2 solution (5.0 ml) of alcohol S-9 (2.30 g, 12.7 mmol) was added over a period of 5 min. To this mixture was added triethylamine (9.76 ml, 70 mmol) at -50 ºC, and the mixtures were stirred for 0.5 h before it was brought to 23 0 C. The reaction mixture was poured into water and the organic layer was extracted with dichloromethane. The extracts were washed with brine, dried over magnesium sulfate, and concentrated. The residues were chromatographed (hexane-ethylacetate, 10:1) on a silica gel to afford the aldehyde. To a THF solution (10 ml) of this aldehyde (1.94 g, 10.8 mmol) was added allylmagnesium bromide (13.0 ml, 13.0 mmol) at 78 ºC and the mixture was stirred at 23 0 C for 8 h. The reaction was quenched with a aqueousnh 4 Cl solution, extracted with diethyl ether, dried over Na 2 S 4. The residues were chromatographed through a silica column (silica gel, hexane-ether 1:1) to give the alcohol S-10 (2.0 g, 9.0 mmol, 84 %). Synthesis of rel-(s)-1-((2r,3s)-3-methyl-3-(oct-1-ynyl)oxiran-2-yl)but-3-en-1-ol (S-11). To a CH 2 Cl 2 solution (20 ml) of allyllic alcohol S-10 (1.00 g, 4.50 mmol) was added m-chloroperbenzoic acid (0.94 g, 5.71 mmol) and the mixtures were stirred at 23 0 C for 8 h. The resulting solution was quenched with NaHC 3 solution, extracted with diethyl ether, and dried over anhydrous MgS 4. The resulting solution was filtered through a small Al 2 3 bed, then concentrated and eluted through a Et 3 N-pretreated silica column S3

4 (diethyl ether-hexane, 1:1) to afford the epoxyalcohol S-11 as a colorless oil (0.90g, 3.82 mmol, 84 %). Synthesis of rel-(s)-1-((2r,3s)-3-methyl-3-(oct-1-ynyl)oxiran-2-yl)but-3-enyl acetate (14). To a CH 2 Cl 2 solution (20 ml) of epoxy alcohol S-11 (1.00g, 4.23 mmol) was added pyridine (1.00 ml, 12.7 mmol) at 0 ºC. After 10 min, the mixture was added acetyl chloride (0.60 ml, 8.43 mmol), and the resulting mixtures were stirred for 2 h. The resulting solution was quenched with water, extracted with diethyl ether, and dried over anhydrous MgS 4. The residues were chromatographed through a short silica bed to afford epoxyalkyne 14 as a color oil (0.95 g, 3.44 mmol, 81.0 %). (C) Synthesis of dimethyl 2-allyl-2-(((2R*,3S*)-3-methyl-3-(oct-1-ynyl)oxiran-2-yl)methyl)malonate (20) n-c 6 H 13 Scheme S-3 E E E Na E m-cpba Br S-7 79% S-12 71% n-c6 H n-c 6 H E E E = C 2 Me Synthesis of (Z)-dimethyl 2-allyl-2-(3-methylundec-2-en-4-ynyl)malonate (S-12). To a THF (50 ml) suspension of NaH (244 mg, 10.0 mmol) was added dimethyl 2-allylmalonate (1.72 g, 10.0 mmol) at 0 o C and stirred for 30 min at same temperature before addition of allyl bromide S-7 (2.04 g, 8.4 mmol). The reaction mixture was stirred for 4 h at 23 o C under a N 2 atmosphere. To the solution was added a NH 4 Cl solution, and the organic layer was extracted with diethyl ether and dried over MgS0 4. The concentrated residues were chromatographed through a silica column (hexane-ether, 1:1) to give diene S-12 as a colorless oil (2.22 g, 6.63 mmol, 79.0 %). Synthesis of dimethyl 2-allyl-2-(((2R*,3S*)-3-methyl-3-(oct-1-ynyl)oxiran-2-yl)methyl)malonate (20). S4

5 To a CH 2 Cl 2 solution (20 ml) of compound S-12 (1.20 g, 3.59 mmol) was added m-chloroperbenzoic acid (0.743 g, 4.3 mmol) and the mixtures were stirred for 12 h at 23 0 C before quenching with a NaHC 3 solution. The organic layer was extracted with diethyl ether, dried over MgS 4. The solution was filtered through a short Al 2 3 bed, then concentrated and eluted through a Et 3 N-pretreated silica column (diethyl ether-hexane, 2:1) to afford epoxyalkyne 20 as a colourless oil (0.90 g, 2.57 mmol, 71%). (2) Spectra data for compounds 1-68: 2-Hex-1-ynyl-3-methoxymethyl-2-methyl-oxirane (1a). IR (neat, cm -1 ): 2242(w); 1 H NMR (400 MHz, CDCl 3 ): δ 3.70 (dd, J = 11.2, 4.4 Hz, 1 H), 3.55 (dd, J = 11.2, 5.6 Hz, 1 H), 3.39 (s, 3 H), 3.02 (t, J = 6.0 Hz, 1 H), 2.18 (t, J = 1.6 Hz, 2 H), 1.53 (s, 3 H), 1.49~1.38 (m, 4 H), (t, J = 1.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 85.9, 81.2, 72.1, 62.5, 59.2, 51.6, 30.6, 23.8, 22.0, 18.5, 13.7; Mass (75 ev, m/z): 182 (M + ). N-Benzyl-4-methyl-N-(3-methyl-3-oct-1-ynyl-oxiranylmethyl)-benzenesulfonami de (1b). IR (neat, cm -1 ): 2239(m), 1627(w); 1 H NMR (400 MHz, CDCl 3 ): δ 7.75 (d, J = 6.8 Hz, 2 H), 7.34~7.24 (m, 7 H), 4.59 (d, J = 14.8 Hz, 1 H), 4.23 (d, J = 15.2 Hz, 1 H), 3.48 (dd, J = 15.2, 4.8 Hz, 1 H), 3.36 (dd, J = 14.8, 6.0 Hz, 1 H), 2.80 (t, J = 4.8 Hz, 1 H), 2.43 (s, 3 H), 2.48 (t, J = 6.0 Hz; 2 H), 1.42~1.19 (m, 4 H), 1.18 (s, 3 H), (t, J = 6.4 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 143.4, 136.7, 136.6, 129.7, 128.4, 128.2, 127.6, 127.2, 86.3, 76.8, 62.2, 52.6, 52.5, 48.1, 31.7, 28.4, 28.2, 22.9, 22.4, 21.4, 18.5, 13.9; Mass (75 ev, m/z): 439 (M + ). 3-Butyl-5-hydroxy-6-methoxymethyl-5-methyl-5,6-dihydro-pyran-2-one (2a). IR (neat, cm -1 ): 3351(vs), 1713(s); 1 H NMR (400 MHz, CDCl 3 ): δ 6.43 (s, 1 H), 4.42 (t, J = 6.8 Hz, 1 H), 3.72 (d, J = 7.2 Hz, 2 H), 3.42 (s, 1 H), 2.28~2.19 (m, 2 H), 1.45~1.27 S5

6 (m, 4 H), 1.25 (s, 3 H), (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 163.8, 147.1, 129.5, 78.6, 70.8, 69.0, 59.6, 29.9, 29.8, 22.1, 21.0, 13.7; HRMS calcd. for C 12 H 20 4 : , Found: N-Benzyl-N-(5-hexyl-3-hydroxy-3-methyl-6-oxo-3,6-dihydro-2H-pyran-2-ylmeth yl)-4-methyl-benzenesulfonamide (2b). IR (neat, cm -1 ): 3351(vs), 1721(s), 1622(w); 1 H NMR (500 MHz, CDCl 3 ): δ 7.66 (d, J = 8.0 Hz, 2 H), 7.25~7.17 (m, 7 H), 6.88 (s, 1 H), 5.19 (t, J = 7.0 Hz, 1 H), 4.26 (s, 2 H), 3.80 (d, J = 6.5 Hz, 2 H), 2.38 (s, 3 H), 2.17 (t, J = 7.5 Hz, 2 H), 1.50 (s, 3 H), 1.35~1.15 (m, 8 H), 0.81 (t, J = 4.0 Hz, 3 H); 13 C NMR (125 MHz, CDCl 3 ): δ 173.1, 143.5, 137.2, 135.6, 135.4, 131.1, 129.7, 128.6, 128.3, 127.9, 127.1, 76.7, 66.0, 50.86, 44.3, 31.5, 29.9, 29.4, 27.3, 22.6, 21.5, 15.9, 14.0; HRMS calcd. for C 27 H 35 N 5 S: , Found: N-Benzyl-N-(5-hexyl-3-methyl-6-oxo-6H-pyran-2-ylmethyl)-4-methyl-benzenesul fonamide (3). IR (neat, cm -1 ): 1713(s), 1622(w); 1 H NMR (500 MHz, CDCl 3 ): δ 7.64 (d, J = 8.5 Hz, 2 H), 7.31~7.22 (m, 7 H), 6.56 (s, 1 H), 4.44 (s, 2 H), 4.06 (s, 2 H), 2.39 (s, 3 H), 2.22 (t, J = 8.5 Hz, 2 H), 1.85 (s, 3 H), 1.29~1.25 (m, 8 H), 0.87 (t, J = 7.0 Hz, 3 H); 13 C NMR (125 MHz, CDCl 3 ): δ 162.1, 150.7, 143.5, 141.9, 136.1, 135.8, 129.6, 128.8, 128.3, 128.2, 127.6, 127.0, 113.8, 52.6, 45.8, 31.5, 30.1, 28.9, 27.7, 22.5, 21.5, 14.6, 14.0; HRMS calcd. for C 27 H 33 N 4 S: , Found: But-3-enyl-2-methyl-2-phenylethynyl-oxirane (4). IR (neat, cm -1 ): 2215(w), 1645(w), 1622(w); 1 H NMR (400 MHz): δ 7.40~7.43 (m, 2 H), 7.25~7.30 (m, 3 H), 5.82~5.92 (m, 1 H), 5.08 (dd, J = 17.6, 3.2 Hz, 1 H), 5.00 (dd, J = 10.8, 2.0 Hz, 1 H), 2.93 (t, J = 6.4 Hz, 1 H), 2.25~2.32 (m, 2 H), 1.85~1.90 (m, 2 H), 1.61 (s, 3 H); 13 C NMR (100 MHz): δ 137.4, 131.8, 128.5, 128.2, 122.2, 115.2, 86.8, 84.1, 64.8, 52.8, 30.1, 29.5, 23.4; Mass (75 ev, m/z): 212 (M + ). rel-(5ar,7ar,7br)-7b-methyl-3-phenyl-2,4,5,5a,6,7,7a,7b-octahydropentaleno[1,6 -bc]pyran-2,4-dione (4a). IR (neat, cm -1 ): 1730(s), 1723(s), 1644(w), 1613(w); 1 H S6

7 NMR (400 MHz): δ 7.34~7.39 (m, 3 H), 7.28~7.31 (m, 2 H), 4.88 (t, J = 8.8 Hz, 1 H), 2.74 (dd, J = 19.6, 8.0 Hz, 1 H), 2.50 (dd, J = 15.6, 9.2 Hz, 1 H), 2.33~2.40 (m, 1 H), 2.27 (d, J = 19.6 Hz, 1 H), 2.02~2.16(m, 2 H), 1.40~1.50 (m, 1 H), 1.44 (s, 3 H); 13 C NMR (100 MHz): δ 203.4, 163.3, 147.2, 132.4, 130.5, 130.3, 129.3, 127.3, 86.8, 48.3, 43.8, 41.2, 30.7, 29.1, 22.4; HRMS Calcd for C 17 H 16 3 : ; Found: rel-(1ar,3ar,6br)-6b-methyl-6-phenyl-1a,2,3,3a,5,6b-hexahydro-1h-4-oxacyclob uta[cd]inden-5-one (4b). IR (neat, cm -1 ): 1729(s), 1642(w), 1622(w); 1 H NMR (400 MHz): δ 7.30~7.36 (m, 2 H), 7.25~7.28 (m, 3 H), 4.58 (t, J = 10.0 Hz, 1 H), 3.71 (dd, J = 16.2, 9.6 Hz, 1 H), 2.60 (d, J = 13.6 Hz, 2 H), 2.14~2.26 (m, 2 H), 1.85~ 1.91 (m, 1 H), 1.68~1.74 (m, 1 H), 1.53 (s, 3 H); 13 C NMR (100 MHz): δ 162.4, 158.3, 132.5, 129.7, 128.3, 128.2, 127.8, 127.6, 86.1, 53.1, 40.8, 39.9, 31.7, 27.4, 17.6; HRMS Calcd for: C 16 H 16 2 : ; Found: But-3-enyl-2-methyl-2-oct-1-ynyl-oxirane (5). IR (neat, cm -1 ): 2234(w), 1642(w); 1 H NMR (400 MHz, CDCl 3 ): δ 5.89~5.79 (m, 1 H), 5.05 (dd, J = 17.2, 1.6 Hz, 1 H), 4.98 (dd, J = 10.4, 1.6 Hz, 1 H), 2.81 (t, J = 6 Hz, 1 H), 2.49~2.16 (m, 4 H), (m, 2 H) 1.48 (s, 3 H), (m, 8 H), 0.86 (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 137.5, 114.9, 85.2, 77.7, 64.3, 52.6, 31.1, 30.0, 29.3, 28.3, 23.6, 22.4, 18.5, 13.8; Mass (75 ev, m/z): 220 (M + ). rel-(5ar,7ar,7br)-3-hexyl-7b-methyl-2,4,5,5a,6,7,7a,7b-octahydropentaleno[1,6- bc]pyran-2,4-dione (5a). IR (neat, cm -1 ): 1725(s), 1710(s), 1622(w); 1 H NMR (400 MHz, CDCl 3 ): δ 4.77 (t, J = 8.0 Hz, 1 H), 2.92~2.85(m,1 H), 2.68 (dd, J = 18.8, 8 Hz,1 H), 2.62~2.57 (m,1 H), 2.42 (q, J = 9.6 Hz, 1 H), 2.31 (d, J = 19.2 Hz, 1 H), 2.31~2.21 (m, 1 H), 2.11~2.01 (m, 1 H), 1.92~1.86 (m, 1 H), 1.29 (s, 3 H), 1.42~1.22 (m, 9 H), 0.84 (t, J = 7.6 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 206.1, 163.7, 146.7, 135.7, 87.1, 48.0, 44.1, 41.5, 31.4, 30.8, 29.3, 29.2, 29.1, 25.6, 22.5, 22.4, 14.0; HRMS calcd for C 17 H 24 3, , Found S7

8 2, (3 CH 3 ); HRMS Calcd For C 14 H 20 2 Si: ; Found: rel-(1ar,3ar,6br)-6-hexyl-6b-methyl-1a,2,3,3a,5,6b-hexahydro-1h-4-oxacyclobu ta[cd]inden-5-one (5b). IR (nujol, cm -1 ): 1712(s), 1610(w); 1 H NMR (500 MHz, CDCl 3 ): δ 4.46 (t, J = 8.5 Hz, 1 H), 3.32 (dd, J = 15, 9 Hz, 1 H), 2.52 (d, J = 15 Hz, 1 H), 2.45 (t, J = 9 Hz,1 H), 2.24~2.06 (4 H, m), 1.92~1.83 (m, 1 H), 1.74~1.70 (m, 1 H), 1.40 (t, J = 7 Hz, 2 H), 1.35 (s, 3 H), 1.24~1.18 (m, 8 H), 0.81 (t, J = 7 Hz, 3 H); 13 C NMR (125 MHz, CDCl 3 ): δ 163.7, 156.5, 123.4, 86.6, 52.1, 40.1, 37.3, 32.1, 31.4, 29.1, 27.9, 27.7, 27.0, 22.5, 17.7, 13.9; HRMS cald. For, C 16 H 24 2, , Found, But-3-enyl-3-phenylethynyl-oxirane (6). IR (neat, cm -1 ): 2251(w), 1642(w); 1 H NMR (400 MHz, CDCl 3 ): δ 7.44~7.42 (m, 2 H), 7.32~7.27 (m, 3 H), 5.81~5.41 (m, 1 H), 5.09(dd, J = 17.2, 1.6 Hz, 1 H), 5.01 (d, J = 10 Hz, 1 H), 3.64 (d, J = 4.4 Hz, 1 H), 3.17~3.13 (m, 1 H), 2.33~2.28 (m, 2 H), 1.91~1.54 (m, 2 H); 13 C NMR (100 MHz, CDCl 3 ): δ , 131.7, 128.5, 128.1, 122.1, 115.0, 85.1, 84.3, 57.6, 45.2, 29.9, 28.7; Mass (75 ev, m/z): 198 (M + ). rel-(5ar,7ar,7br)-3-phenyl-2,4,5,5a,6,7,7a,7b-octahydropentaleno[1,6-bc]pyran- 2,4-dione (6a). IR (neat, cm -1 ): 1720(s), 1711(s), 1623(w), 1612(w); 1 H NMR (400 MHz, CDCl 3 ): δ 7.40~7.30 (m, 5 H), 5.23 (q, J = 8.0 Hz, 1 H), 3.55 (t, J = 7.6 Hz, 1 H), 2.91 (q, J = 7.6 Hz, 1 H), 2.74 (dd, J = 19.6, 8.4 Hz, 1 H), 2.41~2.30 (2 m, H), 2.17~2.05 (m, 2 H), 1.54~1.49 (m, 1 H); 13 C NMR (100 MHz, CDCl 3 ): δ 203.2, 163.4, 142.3, 133.0, 130.4, 129.4, 127.3, 81.1, 45.3, 43.6, 34.6, 31.0, 29.8; HRMS calcd for C 16 H 14 3, , Found Allyloxymethyl-2-methyl-2-oct-1-ynyl-oxirane (7). IR (neat, cm -1 ): 2230(w), 1640(w); 1 H NMR (400 MHz, CDCl 3 ): δ (m, 1 H), 5.32 (d, J = 15.2 Hz, 1 H), 5.18 (d, J = 10.0 Hz, 1 H), 3.98~4.11 (m, 2 H), 3.74 (dd, J = 11.2, 4.8 Hz, 1 H), 3.59 (dd. J = 12.4, 6.0 Hz, 1 H), 3.03 (t, J = 5.2 Hz, 1 H), 2.17 (t, J = 7.2 Hz, 2 H), 1.49 (s, 3 S8

9 H), 1.48~1.24 (m, 9 H), 0.85 (t, J = 4.4 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 134.4, 117.1, 85.6, 72.1, 69.5, 65.7, 62.4, 51.5, 31.2, 28.3, 23.5, 22.4, 18.5, 15.1, 13.9; Mass (75 ev, m/z): 236 (M + ). rel-(2ar,5as,8br)-8-hexyl-8b-methyl-1,2,2a,3,5,5a,7,8b-octahydro-4,6-dioxaacen aphthylene-1,7-dione (7a). IR (neat, cm -1 ): 1730(s), 1716(s), 1642(w); 1 H NMR (400 MHz, CDCl 3 ): δ 4.56 (dd, J = 11.2, 6.4 Hz, 1 H), 4.05 (dd, J = 11.2, 6.0 Hz, 1 H), 3.91 (, dd, J = 12.4, 6.4 Hz, 1 H), 3.18 (t, J = 11.6 Hz, 1 H), 2.99~2.93 (m, 1 H), 2.82 (t, J = 12.4 Hz, 1 H), 2.70~2.64 (m, 2 H), 2.45~2.39 (m, 1 H), 1.99 (d, J = 18.8 Hz, 1 H), 1.34 (s, 3 H), (m, 8 H), (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 204.6, 163.8, 144.1, 138.0, 77.4, 70.1, 64.8, 40.0, 39.6, 38.5, 31.8, 29.4, 29.3, 25.9, 25.3, 22.8, 14.0; HRMS calcd for. C 17 H 24 4 : , Found NE-map of Compound 7a: H 1 nc 6 H Me H 2 H 3 Irradiation Increase (%) H 1 (δ 4.56) Me δ 1.39 (2.27 %) Me (δ 1.39 ) H 1 δ 4.56 (1.98 %) H 2 δ 2.42 (1.92%) H 4 H 2 (δ 2.42) Me δ 1.39 ( 2.54%) H 4 δ 2.66 ( 2.28 %) trans 3-Allyloxymethyl-2-methyl-2-oct-ynyl-oxirane (8) 1 H NMR (400 MHz, CDCl 3 ): δ 5.94~5.85 (m, 1 H), 5.27 (d,1 H, J = 16.0 Hz), 5.19 (d, 1 H, J = 8.9 Hz), 3.97~4.08 (m, 2 H), 3.61 (dd, 1 H, J = 11.6, 4.8 Hz), 3.46 (dd, 1 H, J = 12.0, 5.8 Hz), 3.32 (t, 1 H, J = 5.2 Hz), 2.15 (t, 2 H, J = 7.2 Hz), 1.48~1.20 (m, 11 H), 0.86 (t, 3 H, J = 6.8 Hz). 13 C NMR (100 MHz, CDCl 3 ): δ134.1, 117.4, 83.1, 80.0, 72.0, 67.8, 62.5, 50.6, 31.5, 31.1, 28.3, 28.2, 22.3, 18.9, 18.5, HRMS calcd. for C 15 H 24 2 : , found (3-But-3-enyl-2-methyl-oxiranylethynyl)-trimethylsilane (9). IR (neat, cm -1 ): 1644(w); 1 H NMR (400 MHz): δ 5.78~5.86 (m, 1 H), 5.01 (d, J = 17.2 Hz, 1 H), 4.97 S9

10 (d, J = 8.0 Hz, 1 H), 2.81 (t, J = 6.0 Hz, 1 H), 2.19~2.26 (m, 2 H), 1.73~1.83 (m, 2 H), 1.49 (s, 3 H), (s, 9 H); 13 C NMR (100 MHz): δ 137.3, 114.9, 103.0, 89.2, 64.4, 52.3, 29.9, 29.2, 23.0, (3 CH 3 ); Mass (75 ev, m/z): 208 (M + ). 2-[5-(3-but-3-enyl-2-methyl-oxiranyl)-pent-4-ynyl]-[1,3]dioxolane (10). IR (neat, cm -1 ): 2968 (w); 1 H NMR (400 MHz, CDCl 3 ): δ 5.82~5.76 (m, 1H), 5.04 (dd, J = 16.8, 1.6 Hz, 1H), 4.96 (dd, J = 10.4, 1.6 Hz, 1H), 4.71 (t, J = 6.8 Hz, 1H), 3.97 (t, J = 9.6 Hz, 2H), 3.81 (t, J = 9.6 Hz, 2H), 3.52, 3.41 (AB quartet d, J = 68.4, 12.2 Hz, 1H), 3.13 (t, J = 4.4 Hz, 1H), 2.69 (t, J = 6.2 Hz, 1H), 2.28~2.17 (m, 2H), 1.77~1.58 (m, 4H), 1.43(s, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ 137.0, 114.1, 132.7, 100.7, 82.3, 79.2, 64.7, 63.2, 49.1, 32.6, 29.2, 28.8, 22.4, 21.3, 19.4; MS (75 ev, m/z): 250 (M + ); HRMS calcd for C 15 H 22 3 : , Found (3-butenyl)-2-ethyl-2-(1-hexynyl)oxirane (11). IR (neat, cm -1 ): 2230(w), 1653(w); 1 H NMR (400 MHz, CDCl 3 ): δ 5.92~5.80 (m, 1 H), 5.05 (dd, 1 H, J = 17.2, 1.6 Hz), 4.97 (dd, 1 H, J = 10.4, 1.6 Hz), 2.87 (t, 1 H, J = 6 Hz), 2.25~2.19 (m, 4 H), 1.83~1.55 (m, 4 H), 1.50~1.43 (m, 2 H), 1.41~1.36 (m, 2 H), 1.04 (t, 3 H, J = 7.6 Hz), 0.88 (t, 3 H, J = 7.2 Hz); 13 C NMR (100 MHz, CDCl 3 ): δ 137.6, 115.0, 86.2, 76.7, 63.6, 57.5, 31.2, 30.5, 29.3, 28.5, 22.5, 18.7, 14.0, 9.7; HRMS calcd. for C 14 H 22 : , found but-3-enyl-2-hexyl-2-oct-1-ynyl-oxirane (12). IR (neat, cm -1 ): 2928 (w); 1 H NMR (400 MHz, CDCl 3 ): δ 5.72 (m 1H), 5.06 (dd, J = 16.4, 1.2 Hz, 1H), 4.96 (dd, J = 10.4, 1.2 Hz, 1H), 2.99 (t, J = 7.2 Hz, 1H), 2.42~2.09 (m, 4H), 1.71~1.65 (m, 2H), 1.58~1.42 (m, 8H), 1.42~1.23 (m, 10H), 0.92 (t, J = 6.8 Hz, 6H); 13 C NMR (100 MHz, CDCl 3 ): δ 137.6, 114.9, 86.1, 63.6, 56.6, 37.2, 31.6, 31.2, 30.1, 29.3, 28.9, 28.4, 28.3, 28.2, 27.5, 25.4, 22.4, 19.1, 18.6, 13.9; MS (75 ev, m/z): 290 (M + ); HRMS calcd for C 20 H 34 : , Found S10

11 3-but-3-enyl-2-hexyl-2-phenylethynyl-oxirane (13). IR (neat, cm -1 ): 2963 (w); 1 H NMR (400 MHz, CDCl 3 ): δ 7.41 (d, J = 7.6 Hz, 2H), 7.36~7.30 (m, 3H), 5.90~5.86 (m, 1H), 5.12 (dd, J = 17.6, 1.2 Hz, 1H), 5.06 (dd, J = 10.4, 1.2 Hz, 1H), 2.98 (t, J = 7.0 Hz, 1H), 2.38 (m, 2H), 1.91~1.80 (m, 4H), 1.71~1.62 (m, 4H), 1.42~1.33 (m, 4H), 0.92 (t, J = 6.8 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ 137.5, 132.4, 131.8, 129.1, 128.5, 128.4, 122.3, 115.2, 85.0, 81.5, 64.1, 56.7, 36.9, 31.7, 30.2, 29.4, 28.9, 25.5, 22.5, 14.0; MS (75 ev, m/z): 282 (M + ); HRMS calcd for C 20 H 26 : , Found Acetic acid 1-(3-methyl-3-oct-1-ynyl-oxiranyl)-but-3-enyl ester (14). IR (neat, cm -1 ): 2233(w), 1718(s), 1642(w); 1 H NMR (400 MHz, CDCl 3 ): δ 5.83~5.73 (m, 1 H), 5.11 (d, J = 15.2 Hz, 1 H), 5.08 (d, J = 7.2 Hz, 1 H), 4.92~4.87 (m, 1 H), 2.94 (d, J = 7.8 Hz, 1 H), 2.58~2.44 (m, 2 H), 2.20 (t, J = 4.8 Hz, 2 H), 2.05 (s, 3 H), 1.55~1.27 (m, 11 H), (t, J = 5.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 170.2, 132.6, 118.3, 86.7, 79.2, 73.9, 64.6, 52.2, 36.3, 31.4, 28.6, 28.5, 23.9, 22.6, 21.2, 18.8, 14.2; Mass (75 ev, m/z): 278 (M + ). 3-(1-Methoxy-but-3-enyl)-2-methyl-2-oct-1-ynyl-oxirane (15). IR(neat, cm -1 ): 2243(w), 1644(w); 1 H NMR (300 MHz, CDCl 3 ): δ 5.90~5.78 (m, 1 H), 5.11 (d, J = 15.2 Hz, 1 H), 5.04 (d, J = 7.2 Hz, 1 H), 3.35 (s, 3 H), 3.26~3.19 (m, 1 H), 2.78 (d, J = 7.8 Hz, 1 H), 2.36 (t, J = 7.2 Hz, 1 H), 2.16 (t, J = 7.0 Hz, 1 H), 1.53~1.23 (m, 11 H), (t, J = 6.9 Hz, 3 H); 13 C NMR (75 MHz, CDCl 3 ): δ 134.0, 117.0, 85.8, 80.8, 79.5, 66.5, 57.9, 49.2, 36.5, 31.2, 28.4, 22.5, 23.7, 22.5, 18.6, 14.0; Mass (75 ev, m/z): 250 (M + ). 1-[3-(1-hexynyl)-3-methyloxiran-2-yl]-4-pentenyl acetate (16). IR (neat, cm -1 ): 2236(w), 1718(s), 1645(w); 1 H NMR (400 MHz, CDCl 3 ): δ 5.84~5.74 (m, 1 H), 5.03 (dq, 1 H, J = 17.2, 1.2 Hz), 4.97 (dq, 1 H, J = 10.4, 2.0 Hz), 4.89 (td, 1 H, J = 8.0, 5.2 Hz), 2.89 (d, 1 H, J = 8.0 Hz), 2.18 (t, 2 H, J = 7.2 Hz), 2.18~2.06 (m, 2 H), 2.06 (s, 3 S11

12 H), 1.85~1.70 (m, 2 H), 1.51~1.43 (m, 2 H), 1.50 (s, 3 H), 1.40~1.34 (m, 2 H), 0.88 (t, 3 H, J = 7.6 Hz); 13 C NMR (100 MHz, CDCl 3 ): δ 169.7, 137.2, 114.8, 86.0, 76.7, 74.0, 64.6, 51.7, 30.5, 30.1, 28.7, 23.5, 21.6, 20.7, 18.1, 13.2; HRMS calcd. for C 16 H 24 3 : , found allyloxymethyl-2-hex-1-ynyl-2-methyl-oxirane (17). IR (neat, cm -1 ): 2902 (w); 1 H NMR (400 MHz, CDCl3): δ 5.85~5.94 (m, 1 H), 5.32 (d, J = 15.2Hz, 1 H), 5.18 (d, J = 10.0 Hz, 1 H), 3.98~4.11 (m, 2 H), 3.74 (dd, J = 11.2, 4.8 Hz, 1 H), 3.59 (dd. J = 12.4, 6.0 Hz, 1 H), 3.03 (t, J = 5.2 Hz, 1 H), 2.17 (t, J = 7.2 Hz, 2H), 1.49 (s, 3H), 1.48~1.24 (m, 4 H), 0.85 (t, J = 6.4 Hz, 3 H); 13 C NMR (100 MHz, CDCl3): δ 134.4, 117.1, 85.6, 72.1, 69.5, 65.7, 62.4, 51.5, 31.2, 28.3, 23.5, 22.4, 18.5, 15.1, 13.9; MS (75 ev, m/z): 208 (M + ); HRMS calcd for C 13 H 20 2 : , Found N-Allyl-4-methyl-N-(3-methyl-3-oct-1-ynyl-oxiranylmethyl)-benzenesulfonamide (18). IR (neat, cm -1 ): 2235(w), 1643(w); 1 H NMR (400 MHz): δ 7.69 (d, J = 8.0 Hz, 2 H), 7.26 (d, J = 8.0 Hz, 2 H), 5.63~5.67 (m, 1 H), 5.18 (d, J = 17.6 Hz, 1 H), 5.11 (d, J = 10.4 Hz, 1 H), 3.87, 3.84 (ABq, J = 14.0, 6.0 Hz, 2 H), 3.47 (dd, J = 14.6, 4.8 Hz, 1H), 3.31 (dd, J = 15.4, 5.2 Hz, 1 H), 2.96 (t, J = 5.0 Hz, 1 H), 2.38 (s, 3 H), 2.12 (t, J = 7.0 Hz, 2 H), 1.32~1.43 (m, 4 H), 1.21~1.30 (m, 4 H), 0.82 (t, J = 5.4 Hz, 3 H); 13 C NMR (100 MHz): δ 143.2, 137.2, 133.0, 129.6, 127.3, 127.2, 118.5, 86.3, 62.5, 52.2, 51.3, 47.9, 31.1, 28.4, 28.3, 23.3, 22.3, 21.3, 18.6, 13.7; Mass (75 ev, m/z): 389 (M + ). N-allyl-N-(3-hex-1-ynyl-3-methyl-oxiranylmethyl)-4-methyl-benzenesulfonamide (19). IR (neat, cm -1 ): 2948 (w); 1 H NMR (400 MHz, CDCl 3 ): δ 7.68 (d, J = 8.0 Hz, 2H), 7.25 (d, J = 8.0 Hz, 2H), 5.64~5.66 (m, 1H), 5.17 (d, J = 17.6 Hz, 1H), 5.10 (d, J = 10.4 Hz, 1H), 3.86, 3.83 (AB quartet d, J = 14.0, 6.0 Hz, 2H), 3.47, 3.31 (AB quartet d, J = 65.6, 14.6 Hz, 2H), 2.95 (t, J = 5.0 Hz, 1H), 2.37 (s, 3H), 2.02 (s, 3H), 2.12 (t, J = 7.0 Hz, 2H), 1.21~1.30 (m, 4H), 0.81 (t, J = 6.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ S12

13 143.2, 137.2, 133.0, 129.6, 127.3, 127.2, 118.5, 86.4, 62.5, 52.2, 51.3, 47.9, 31.1, 28.4, 28.3, 23.3, 22.3, 21.3, 18.6, 13.7; MS (75 ev, m/z): 361 (M + ); HRMS calcd for C 20 H 27 N 3 S: , Found Allyl-2-(3-methyl-3-oct-1-ynyl-oxiranylmethyl)-malonic acid dimethyl ester (20). IR (neat, cm -1 ): 2231(w), 1715(s), 1640(w); 1 H NMR (400 MHz, CDCl 3 ): δ 5.74~5.61 (m, 1 H), 5.09 (d, J = 11.2 Hz, 1 H), 5.06 (d, J = 1.6 Hz, 1 H), 3.71 (s, 6 H), 2.90 (t, J = 6.0 Hz, 1 H), 2.70 (t, J = 7.2 Hz, 2 H), 2.22 (d, J = 6.0 Hz, 2 H), 2.16 (t, J = 6.8 Hz, 2 H), 1.44 (s, 3 H), 1.31~1.22 (m, 8 H), (t, J = 6.9 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 171.1, 132.1, 119.4, 85.9, 76.8, 61.1, 56.2, 52.6, 52.5, 52.4, 38.5, 33.8, 31.2, 28.3, 23.6, 22.4, 18.6, 13.9; Mass (75 ev, m/z): 350 (M + ). 2-Allyl-2-(3-oct-1-ynyl-oxiranylmethyl)-malonic acid dimethyl ester (21). IR (neat, cm -1 ): 2241(w), 1734(w), 1643(w); 1 H NMR (300 MHz, CDCl 3 ): δ 5.71~5.62 (m, 1 H), 5.11 (d, J = 9.4 Hz, 1 H), 5.07 (s, 1 H), 3.71 (s, 6 H), 3.37 (dd, J = 3.8, 1.6 Hz, 1 H), 3.11~3.06 (m, 1 H), 2.73 (d, J = 7.2 Hz, 2 H), 2.28 (dd, J = 15.2, 6.0 Hz, 1 H), 2.20~2.12 (m, 3 H), 1.52~1.42 (m, 2 H), 1.36~1.25 (m, 6 H), (t, J = 6.9 Hz, 3 H); 13 C NMR (75 MHz, CDCl 3 ): δ 171.3, 132.3, 119.7, 87.5, 74.5, 56.5, 54.5, 52.8, 52.7, 45.4, 38.6, 33.2, 31.5, 28.7, 28.5, 22.7, 18.9, 14.2; Mass (75 ev, m/z): 336 (M + ). 2-But-3-enyl-3-oct-1-ynyl-oxirane (22). IR (neat, cm -1 ): 2233(w), 1640(w); 1 H NMR (400 MHz, CDCl 3 ): δ (m, 1 H), 5.06 (d, J = 18.8 Hz, 1 H), 4.99 (d, J = 9.6 Hz, 1 H), 3.41~3.39 (m, 1 H), 3.01~2.98 (m, 1 H), 2.28~2.18 (m, 4 H), 1.84~1.69 (m, 2 H), 1.53~1.21 (m, 8 H), (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 137.4, 115.0, 86.4, 74.8, 57.2, 45.3, 31.2, 30.0, 28.5, 28.3, 28.26, 22.4, 18.6, 13.9; Mass (75 ev, m/z): 206 (M + ). [3-(1,1-dimethyl-but-3-enyl)-oxiranylethynyl]-trimethyl-silane (23). IR (neat, cm -1 ): S13

14 2261 (w), 1638(m); 1 H NMR (400 MHz, CDCl 3 ): δ 5.83 (m, 1H), 5.05 (s, 1H), 5.02 (d, J = 8.0 Hz, 1H,), 3.31, 2.79 (AB quartet d, J = 207.6, 4.4 Hz, 1H), 2.23~2.12 (m, 2H), 1.06 (s, 6H), 0.13 (s, 9H); 13 C NMR (100 MHz, CDCl 3 ): δ 134.6, 117.8, 108.1, 93.8, 65.6, 45.8, 45.1, 43.9, 24.4, 23.3, -0.3; MS (75 ev, m/z): 222 (M + ); HRMS calcd for C 13 H 22 Si: , Found Acetic acid 1-(3-oct-1-ynyl-oxiranyl)-but-3-enyl ester (24). IR (neat, cm -1 ): 2230(w), 1722(s), 1640(w); 1 H NMR (400 MHz, CDCl 3 ): δ 5.83~5.72 (m, 1 H), 5.18 (d, J = 8.0 Hz, 1H), 5.15 (d, J = 9.6 Hz, 1 H), 4.98~4.92 (m, 1 H), 3.53~3.51(m, 1 H), 3.10 (dd, J = 8.4, 4.0 Hz, 1 H), 2.58~2.43 (m, 2 H), 2.22~2.18 (m, 2 H), 2.09 (s, 3 H), 1.54~1.20 (m, 8 H), (t, J = 6.0 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 170.3, 132.4, 118.6, 88.1, 73.9, 73.5, 58.1, 44.6, 36.1, 31.4, 28.7, 28.4, 22.7, 21.3, 18.9, 14.2; Mass (75 ev, m/z): 264 (M + ). 1-[3-(1-octynyl)oxiran-2-yl]-4-pentenyl acetate (25). IR (neat, cm -1 ): 2233(w), 1725(s), 1642(w); 1 H NMR (400 MHz, CDCl 3 ): δ 5.84~5.74 (m, 1 H), 5.02 (dq, 1 H, J = 17.6, 2.0 Hz), 4.97 (dq, 1 H, J = 10.4, 2.0 Hz), 4.91 (td, 1 H, J = 8.0, 5.2 Hz), 3.51~3.49 (m, 1 H), 3.09 (dd, 1 H, J = 8.0, 4.4 Hz), 2.19 (td, 2 H, J = 6.8, 1.6 Hz), 2.16~2.06 (m, 2 H), 2.08 (s, 3 H), 1.85~1.74 (m, 2 H), 1.48 (quin, 2 H, 8.0 Hz), 1.39~1.22 (m, 6 H), 0.86 (t, 3 H, J = 6.8 Hz); 13 C NMR (100 MHz, CDCl 3 ): δ 169.9, 137.2, 114.9, 87.6, 73.8, 73.6, 58.1, 44.3, 31.1, 30.4, 28.7, 28.3, 28.1, 22,3, 20.9, 18.6, 13.8; HRMS calcd. for C 17 H 26 3 : , found Allyloxymethyl-3-hex-1-ynyl-oxirane (26). IR (neat, cm -1 ): 2230(w), 1641(w); 1 H NMR (400 MHz, CDCl 3 ): δ ~5.81 (m, 1 H), 5.28 (d, J = 17.2 Hz, 1 H), 5.18 (d, J = 10 Hz, 1 H), 4.11~3.97 (m, 2 H), 3.76 (dd, J = 11.6, 4.8 Hz, 1 H), 3.60 (dd, J = 11.2, 6 Hz, 1 H), 3.47~3.46 (m, 1 H), 3.23~3.20 (m, 1 H), 2.19 (t, J = 6.8 Hz, 2 H), 1.49~1.32 (m, 4 H), 0.88 (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 134.1, 116.7, 86.4, 74.0, 71.8, 68.8, 55.4, 43.6, 30.0, 21.4, 18.0, 13.1; Mass (75 ev, m/z): 194 (M + ). S14

15 N-Allyl-4-methyl-N-(3-oct-1-ynyl-oxiranylmethyl)-benzenesulfonamide (27). IR (neat, cm -1 ): 2230(w), 1618(w); 1 H NMR (400 MHz): δ 7.69 (d, J = 8.0 Hz, 2 H), 7.26 (d, J = 8.0 Hz, 2 H), 5.69~5.61 (m, 1 H), 5.18 (d, J = 16.8 Hz, 1 H), 5.12 (d, J = 10.4 Hz, 1 H), 3.86~3.88 (m, 2 H), 3.52 (dd, J = 14.8, 4.4 Hz, 1 H), 3.29 (dd, J = 15.6, 6.0 Hz, 1 H), 3.37 (d, J = 4.4 Hz, 1 H), 3.11 (t, J = 6.2 Hz, 1 H), 2.38 (s, 3 H), 2.14 (t, J = 7.2 Hz, 2 H), 1.37~1.44 (m, 2 H), 1.22~1.33(m, 6 H), 0.83(t, J = 6.8 Hz, 3 H); 13 C NMR (100 MHz): δ 143.3, 136.9, 132.7, 129.6, 127.1, 118.8, 87.6, 74.0, 55.7, 51.2, 47.0, 44.6, 31.1, 28.4, 28.1, 22.4, 21.4, 18.6, 13.9; Mass (75 ev, m/z): 375 (M + ). rel-(5ar,7ar,7br)-7b-methyl-3-(1,1,1-trimethylsilyl)-2,4,5,5a,6,7,7a,7b-octahydro pentaleno[1,6-bc]pyran-2,4-dione (29). IR (neat, cm -1 ): 1723(s), 1710(s), 1626(w); 1615(w); 1 H NMR (400 MHz): δ 4.74 (t, J = 8.2 Hz, 1 H), 2.66 (dd, J = 19.6, 8.0 Hz, 1 H), 2.44 (dd, J = 15.6, 9.2 Hz, 1 H), 2.28 (d, J = 19.6 Hz, 1 H), 2.19~2.27 (m, 1 H), 2.05~2.13 (m, 1 H), 1.79~1.87 (m, 1 H), 1.32~1.38 (m, 1 H), 1.25 (s, 3 H), 0.22 (s, 9 H); 13 C NMR (100 MHz): δ 207.2, 162.7, 138.5, 123.2, 86.9, 51.8, 43.1, 39.8, 30.2, 29.7, 21. rel-(5ar,7ar,7br)-3-[3-(1,3-dioxolan-2-yl)propyl]-7b-methyl-2,4,5,5a,6,7,7a,7b-o ctahydropentaleno[1,6-bc]pyran-2,4-dione (30). IR (neat, cm -1 ): 1718 (w); 1 H NMR (500 MHz, CDCl 3 ): δ 4.83 (t, J = 4.5 Hz, 1H), 4.78 (t, J = 8.5 Hz, 1H), 3.92 (t, J = 7.2 Hz, 2H), 3.81 (t, J = 7.2 Hz, 2H), 2.91 (m, 1H), 2.69 (m, 2H), 2.42 (q J = 7.2 Hz, 1H), 2.31 (d, J = 16.2 Hz, 1H), 2.25 (m, 1H), 2.05 (m, 1H), 1.64 (m, 4H), 1.38 (m, 2H),1.29 (s, 3H); 13 C NMR (125 MHz, CDCl 3 ): δ 206.1, 163.6, 147.2, 134.8, 104.1, 87.1, 64.8, 48.0, 44.0, 41.4, 33.4, 30.7, 29.2, 25.3, 23.6, 22.4; MS (75 ev, m/z): 306 (M + ); HRMS calcd for C 17 H 22 5 : , Found rel-(5ar,7ar,7br)-3-butyl-7b-ethyl-2,4,5,5a,6,7,7a,7b-octahydropentaleno[1,6-bc ]pyran-2,4-dione (31). IR (neat, cm -1 ): 1723(s), 1712(s), 1625(w); 1 H NMR (600 MHz, CDCl 3 ): δ 4.84 (t, 1 H, J = 8.2 Hz), 2.89~2.85(m, 1 H), 2.66 (dd, 2 H, J = 19.6, S15

16 8.2 Hz), 2.49~2.47 (m, 1 H), 2.27 (dd, 1 H, J = 19.6, 1.3 Hz), 2.27~2.22 (m, 1 H), 2.06~1.94 (m,1 H), 1.92~1.86 (m,1 H), 1.68~1.55 (m, 3 H), 1.43~1.38 (m, 2 H), 1.32 (quin, 2 H, J = 7.6 Hz), 0.91 (t, 3 H, J = 7.6 Hz), 0.88 (t, 3 H, J = 7.6 Hz); 13 C NMR (150 MHz, CDCl 3 ): δ 206.6, 163.9, 145.5, 136.3, 85.3, 51.4, 44.4, 39.9, 31.7, 31.3, 29.7 (2 x CH), 25.6, 22.7, 13.8, 8.9; HRMS calcd. for C 16 H 22 3 : , found rel-(5ar,7ar,7br)-3,7b-dihexyl-2,4,5,5a,6,7,7a,7b-octahydropentaleno[1,6-bc]pyr an-2,4-dione (32). IR (neat, cm -1 ): 1719(s); 1 H NMR(CDCl 3, 400MHz): δ 4.82 (t, J = 8.8 Hz, 1H), 2.86 (m, 1H), 2.66 (dd, J = 19.2, 1.2 Hz, 1H), 2.63 (m, 1H), 2.47 (m, 1H), 2.25 (dd, J = 18.2, 1.2 Hz, 1H), 2.23 (m, 1H), 2.02 (m, 1H), 1.87 (m, 1H), 1.59~1.51 ( m, 3H), 1.41~1.38 (m, 3H), 1.29~1.19 (m, 13H), 0.83 (t, J = 6.8 Hz, 6H); 13 C NMR(CDCl 3, 100MHz): δ 206.6, 163.9, 145.8, 136.0, 85.6, 51.0, 44.4, 40.2, 37.0, 32.2, 31.6, 31.5, 31.2, 29.6, 29.4, 29.1, 28.0, 25.7, 24.9, 24.4, 22.5, 14.0, 13.9; MS (75 ev, m/z): 346 (M + ); HRMS calcd for C 22 H 34 3 : , Found rel-(5ar,7ar,7br)-7b-hexyl-3-phenyl-2,4,5,5a,6,7,7a,7b-octahydropentaleno[1,6- bc]pyran-2,4-dione (33). IR (neat, cm -1 ): 1726 (s); 1 H NMR(CDCl 3, 400MHz): δ 7.33 (m, 3H), 7.26 (d, J = 7.2 Hz, 2H), 4.87 (t, J = 8.8 Hz, 1H), 2.67 (dd, J = 19.2, 8.4 Hz, 1H), 2.51 (m, 1H), 2.28 (m, 1H), 2.27 (dd, J = 19.2, 1.2 Hz, 1H), 2.04~2.00 (m, 3H), 1.70~1.60 ( m, 2H), 1.46~1.15 (m, 8H), 0.80 (t, J = 6.8 Hz, 3H); 13 C NMR(CDCl 3, 100MHz): δ 203.8, 163.5, 146.7, 132.9, 130.6, 130.5, 129.5, 128.0, 127.9, 127.4, 85.5, 51.4, 44.3, 39.9, 37.4, 31.5, 31.2, 31.0, 29.6, 24.6, 22.5, 14.0; MS (75 ev, m/z): 338 (M + ); HRMS calcd for C 22 H 26 3 : , Found rel-(5ar,7s,7as,7br)-3-hexyl-7b-methyl-2,4-dioxo-2,4,5,5a,6,7,7a,7b-octahydrop entaleno[1,6-bc]pyran-7-yl acetate (34). IR (neat, cm -1 ): 1728(s), 1706(s), 1622(w); 1 H NMR (400 MHz, CDCl 3 ): δ 5.16~5.12 (m, 1 H), 4.77 (d, J = 6.0 Hz, 1 H), 2.81~2.61 (m, 4 H), 2.34 (d, J = 19.6 Hz, 1 H), 2.07 (s, 3 H), 2.01~1.98 (m, 2 H), S16

17 1.42~1.27 (m, 11 H), (t, J = 6.4 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 204.9, 170.2, 162.8, 146.7, 136.4, 89.9, 78.2, 46.0, 43.9, 39.3, 36.4, 31.4, 29.1, 25.9, 22.6, 22.4, 20.8, 14.0; Mass (12 ev, EI): 334. Anal. calcd for Anal. calcd for C 19 H 26 5 : C, 68.24; H, Found, C, 68.02, H, rel-(5ar,7s,7as,7br)-3-hexyl-7-methoxy-7b-methyl-2,4,5,5a,6,7,7a,7b-octahydro pentaleno[1,6-bc]pyran-2,4-dione (35). IR (neat, cm -1 ): 1728(s), 1700(s), 1622(w); 1 H NMR (400 MHz, CDCl 3 ): δ 4.63 (d, J = 4.4 Hz, 1 H), 3.87~3.84 (m, 1 H), 3.37 (s, 3 H), 2.87~2.85 (m, 1 H), 2.70 (d, J = 7.2 Hz, 1 H), 2.64~2.62 (m, 2 H), 2.31 (d, J = 18.4 Hz, 1 H), 2.13~2.06 (m, 1 H), 1.72~1.61 (m, 2 H), 1.40~1.27 (m, 11 H), (t, J = 6.8 Hz, 1 H); 13 C NMR (100 MHz, CDCl 3 ): δ 205.5, 163.2, 146.9, 136.0, 92.7, 85.8, 57.4, 47.1, 43.5, 39.9, 36.9, 31.4, 29.1, 25.6, 22.5, 14.0; HRMS calcd. for C 18 H 26 4 : , Found: rel-(5ar,8s,8as,8br)-3-hexyl-8b-methyl-2,4-dioxo-4,5,5a,6,7,8,8a,8b-octahydro-2 H-cyclopenta[de]chromen-8-yl acetate (36). IR (neat, cm -1 ): 1732(s), 1720(s), 1700(w) 1040 (s); 1 H NMR (500 MHz, CDCl 3 ): δ 4.90~4.85 (m, 1 H), 4.30 (d, 1 H, J = 7.6 Hz), 2.32~2.96 (m, 1 H), 2.67 (dd, 1 H, J = 15.6, 7.2 Hz), 2.65~2.61 (m, 1 H), 2.16 (d, 1 H, J = 15.6 Hz), 2.17~2.13 (m, 1 H), 2.10 (s, 3 H), 1.94~1.91 (m, 2 H), 1.49~1.30 (m, 5 H), 1.39 (s, 3 H), 1.07~1.01 (m, 1 H), 0.89 (t, 3 H, J = 7.6 Hz); 13 C NMR (125 MHz, CDCl 3 ): δ 205.0, 170.4, 163.4, 144.8, 138.0, 85.0, 71.5, 44.3, 43.3, 39.4, 31.2, 28.8, 28.0, 25.4, 25.3, 22.7, 21.1, 13.7; HRMS calcd. for C 18 H 24 5 : , found rel-(2ar,5as,8br)-8-butyl-8b-methyl-1,2,2a,3,5,5a,7,8b-octahydro-4,6-dioxaacen aphthylene-1,7-dione (37). IR (neat, cm -1 ): 1730 (s); 1 H NMR (400 MHz, CDCl3): δ 4.56 (dd, J = 11.2, 6.4 Hz, 1 H), 4.05 (dd, J = 11.2, 6.0 Hz, 1 H), 3.91 (dd, J = 12.4, 6.4 Hz, 1 H), 3.18 (t, J = 11.6 Hz, 1 H), 2.99~2.93 (m, 1 H), 2.82 (t, J = 12.4 Hz, 1 H), 2.70~2.64 (m, 2 H), 2.45~2.39 (m, 1 H), 1.99 (d, J = 18.8 Hz, 1 H), 1.34 (s, 3 H), S17

18 1.36~1.15 (m, 8 H), 0.85 (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl3): δ 204.5, 163.2, 143.7, 137.7, 77.4, 69.6, 65.7, 39.7, 39.2, 38.2, 31.4, 25.3, 24.9, 22.7, 13.7; MS (75 ev, m/z): 264 (M + ); HRMS calcd for C 15 H 20 4 : , Found rel-(2ar,5as,8br)-8-hexyl-8b-methyl-4-[(4-methylphenyl)sulfonyl]-2,2a,3,4,5,5a, 7,8b-octahydro-1H-6-oxa-4-azaacenaphthylene-1,7-dione (38). IR (neat, cm -1 ): 1729(s), 1720(s), 1636(w); 1 H NMR (400 MHz): δ 7.56 (d, J = 8.0 Hz, 2 H), 7.30 (d, J = 8.0 Hz, 2 H), 4.66 (dd, J = 11.0, 6.4 Hz, 1 H), 4.00 (dd, J = 16.1, 6.4 Hz, 1 H), 3.77 (dd, J = 16.1, 6.4 Hz, 1 H), 2.82~2.77 (m, 1 H), 2.71 (dd, J = 19.2, 7.2 Hz, 1 H), 2.48~2.61 (m, 2 H), 2.39 (s, 3 H), 2.10 (dd, J = 22.8, 13.2 Hz, 2 H), 1.68 (t, J = 12.0 Hz, 1 H), 1.38 (s, 3 H), 1.22~1.12 (m, 8 H), 0.85~0.78 (m, 3 H); 13 C NMR (100 MHz): δ 203.9, 162.8, 144.4, 143.2, 137.8, 132.6, 130.0, 127.5, 78.6, 48.7, 46.1, 40.9, 40.3, 38.4, 31.3, 29.1, 28.9, 25.4, 24.9, 22.3, 21.5, 14.0; HRMS Calcd For C 24 H 31 N 5 S: ; Found: NE-map of Compound 38: H 1 nc 6 H Me N-Ts H 2 Irradiation Increase (%) H 1 (δ 4.66 ) Me δ 1.38 ( 2.99 %) H 3 Me (δ 1.38) H 1 δ 4.66 ( 2.07 %) H 2 δ 2.52 ( 1.80 %) H 4 H 2 (δ 2.52 ) Me δ 1.38 ( 2.77 %) H 4 δ 2.72 ( 3.4 %) rel-(2ar,5as,8br)-8-butyl-8b-methyl-4-[(4-methylphenyl)sulfonyl]-2,2a,3,4,5,5a, 7,8b-octahydro-1H-6-oxa-4-azaacenaphthylene-1,7-dione (39). IR (neat, cm -1 ): 1721 (w); 1 H NMR (400 MHz, CDCl 3 ): δ 7.55 (d, J = 8.0 Hz, 2 H), 7.29 (d, J = 8.0 Hz, 2 H), 4.65 (q, J = 13.2 Hz, 1 H), 3.99 (dq, J = 16.1, 2.0 Hz, 1 H), 3.76 (dq, J = 16.1, 2.0 Hz, 1 H), 2.79 (m, 1 H), 2.70 (dd, J = 19.2, 7.2 Hz, 1 H), 2.47~2.60 (m, 2 H), 2.38 (s, 3 H), 2.09 (dt, J = 22.8, 13.2 Hz, 2 H), 1.67 (t, J = 12.0 Hz, 1 H), 1.37 (s, 3 H), 1.21~1.11 (m, 4 H), 0.84 (t, J = 6.8 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 203.9, 161.8, 144.4, 143.2, 137.8, 132.3, 130.0, , 78.6, 48.7, 46.1, 41.0, 40.3, 38.4, 31.2, 25.1, 24.8, S18

19 22.4, 21.5, 13.7; HRMS calcd. for C 22 H 27 N 5 S: , Found: Dimethyl el-(5ar,8ar,8br)-3-hexyl-8b-methyl-2,4-dioxo-4,5,5a,6,7,8,8a,8boctahydro-2h-cyclopenta[de]chromene-7,7-dicarboxylate (40). IR (neat, cm -1 ): 1720(s), 1714(s), 1628(w); 1 H NMR (500 MHz, CDCl 3 ): δ 4.68 (dd, J = 12.0, 5.5 Hz, 1 H), 3.77 (s, 3 H), 3.69 (s, 3 H), 2.93~2.90 (m, 1 H), 2.77~2.66 (m, 3 H), 2.41~2.31 (m, 2 H), 2.01 (d, J = 19.5 Hz, 1 H), 1.69 (t, J = 12.5 Hz, 1 H), 1.42~1.11 (m, 11 H), (t, J = 7.0 Hz, 3 H); 13 C NMR (125 MHz, CDCl 3 ): δ 204.9, 170.3, 169.8, 163.5, 144.4, 137.6, 79.8, 53.6, 53.2, 53.0, 44.1, 40.7, 36.5, 34.8, 32.7, 31.4, 29.25, 29.21, 25.5, 25.0, 22.5, 14.0; HRMS calcd. for C 22 H 30 7 : , Found: NE-map of compound 40. H 1 nc 6 H C 2 Me C 2 Me Me H 2 H 3 Irradiation Increase (%) H 1 (δ 4.68) Me δ 1.25 ( 3.44%) Me (δ 1.25) H 4 H 2 (δ 2.31) H 1 δ 4.68 ( 2.19 %) H 2 δ 2.31 ( 2.02 %) Me δ 1.25 ( 2.18 %) H 4 δ 2.01( 2.34 %) Dimethyl rel-(5ar,8ar,8br)-3-hexyl-2,4-dioxo-4,5,5a,6,7,8,8a,8b-octahydro-2hcyclopenta[de]chromene-7,7-dicarboxylate (41). IR (neat, cm -1 ): 1720(s), 1711(s), 1612(w); 1 H NMR (400 MHz, CDCl 3 ): δ 5.02~4.95 (m, 1 H), 3.76 (s, 3 H), 3.69 (s, 3 H), 3.33~3.32 (m, 1 H), 2.70~2.53 (m, 4 H), 2.29 (d, J = 17.2 Hz, 2 H), 1.73 (t, J = 12.4 Hz, 1 H), 1.40~1.16 (m, 8 H), (t, J = 6.8 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 204.6, 170.6, 170.0, 164.0, 139.3, 138.6, 73.9, 54.3, 53.4, 53.2, 46.6, 38.3, 33.1, 31.7, 31.5, 30.1, 29.4, 29.3, 25.8, 22.7, 14.2; HRMS calcd. for C 21 H 28 7 : , Found: rel-(5ar,7ar,7br)-3-pentyl-2,4,5,5a,6,7,7a,7b-octahydropentaleno[1,6-bc]pyran-2,4-dione (42). IR (neat, cm -1 ): 1720(s), 1711(s), 1623(w); 1 H NMR (400 MHz, CDCl 3 ): δ 5.12 (q, J = 8 Hz, 1 H), 3.31 (t, J = 6.8 Hz, 1 H), 2.91~2.77 (m, 2 H), 2.70~2.59 (m, 2 H), 2.35 (d, J = 19.2 Hz, 1 H), 2.28~2.19 (m, 1 H), 2.08~1.88 (m, 2 H), 1.48~1.17 (m, S19

20 9 H), (t, J = 6 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 206.0, 163.8, 141.5, 136.3, 81.3, 45.4, 43.4, 35.1, 31.4, 31.1, 29.8, 29.2, 29.1, 25.6, 22.4, 13.9; HRMS calcd for. C 16 H 22 3 : , Found rel-(5ar,7as,7br)-7,7-dimethyl-3-(1,1,1-trimethylsilyl)-2,4,5,5a,6,7,7a,7b-octahy dropentaleno[1,6-bc]pyran-2,4-dione (43). IR (neat, cm -1 ): 1722 (w); 1 H NMR (500 MHz, CDCl 3 ): δ 4.70 (t, J = 8.5 Hz, 1H), 3.28 (t, J = 7.5 Hz, 1H), 2.83 (m, 1H), 2.52 (dd, J = 19.5, 7.5 Hz, 1H), 2.26 (d, J = 19.0 Hz, 1H), 1.86 (q, J = 14.0 Hz, 1H), 1.26 (t, J = 12.0 Hz, 1H), 1.11 (s, 3H), 0.98 (s, 3H), 0.22 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ): δ 206.6, 165.7, 157.6, 139.7, 88.7, 48.0, 45.6, 43.3, 42.0, 34.2, 30.7, 26.9, -0.2; MS (75 ev, m/z): 292 (M + ); HRMS calcd for C 16 H 24 3 Si: , Found rel-(5ar,7s,7as,7br)-3-hexyl-2,4-dioxo-2,4,5,5a,6,7,7a,7b-octahydropentaleno[1, 6-bc]pyran-7-yl acetate (44). IR (neat, cm -1 ): 1720(s), 1711(s), 1612(w); 1 H NMR (500 MHz, CDCl 3 ): δ 5.22 (q, J = 6.5 Hz, 1 H), 5.06 (dd, J = 7.5, 6.0 Hz, 1 H), 3.42 (t, J = 6.4 Hz, 1 H), 3.08~2.98 (m, 1 H), 2.82~2.79 (m, 1 H), 2.66 (dd, J = 19.0, 8.0 Hz, 2 H), 2.38 (d, J = 19.5 Hz, 1 H), 2.05 (s, 3 H), 1.99 (t, J = 8.0 Hz, 2 H), 1.43~1.38 (m, 2 H), 1.29~1.18 (m, 6 H), (t, J = 6.8 Hz, 3 H); 13 C NMR (125 MHz, CDCl 3 ): δ 204.7, 170.2, 162.9, 141.4, 137.2, 84.7, 78.6, 45.3, 41.3, 36.7, 32.9, 31.4, 29.3, 29.2, 26.0, 22.5, 20.8, 14.0; HRMS calcd. for C 18 H 24 5 : , Found: rel-(5ar,8s,8as,8br)-3-hexyl-2,4-dioxo-4,5,5a,6,7,8,8a,8b-octahydro-2h-cyclope nta[de]chromen-8-yl acetate (45). IR (neat, cm -1 ): 1735(s), 1725(s), 1708(w) 1035 (s); 1 H NMR (400 MHz, CDCl 3 ): δ 4.94 (td, 1 H, J = 8.4, 6.0 Hz), 4.59 (t, 1 H, J = 8.4 Hz), 3.49 (t, 1 H, J = 4.8 Hz), 2.97~2.90 (m, 1 H), 2.68~2.62 (m, 1 H), 2.57~2.48 (m, 2 H), 2.28 (d, 1 H, J = 17.6 Hz), 2.05 (s, 3 H), 1.94~1.91 (m, 1 H), 1.85~1.79 (m, 1 H), 1.49~1.19 (m, 9 H), 1.14~1.03(m, 1 H), 0.83 (t, 3 H, J = 6.0 Hz); 13 C NMR (100 MHz, CDCl 3 ): δ 204.6, 170.3, 163.6, 139.6, 138.5, 79.0, 70.6, 46.4, 40.3, 32.6, 31.3, 29.2, 28.9, 28.0, 27.2, 25.5, 22.4, 20.9, 13.9; HRMS calcd. for C 19 H 26 5 : , found S20

21 rel-(2ar,5as,8br)-8-butyl-1,2,2a,3,5,5a,7,8b-octahydro-4,6-dioxaacenaphthylene- 1,7-dione (46). IR (neat, cm -1 ): 1720(s), 1711(s), 1610(w); 1 H NMR (400 MHz, CDCl 3 ): δ 4.90~4.84 (m, 1 H), 4.00 (dd, J = 11.6, 6.0 Hz, 1 H), 3.89 (dd, J = 11.2, 5.6 Hz, 1 H), 3.52 (t, J = 6.4 Hz, 1 H), 3.25 (t, J = 11.6 Hz, 1 H), 3.02~2.95 (m, 1 H), 2.90~2.67 (m, 3 H), 2.51 (dd, J = 18.4, 6.8 Hz, 1 H), 2.14 (d, J = 18.4, 1 H), 1.44~1.31 (m, 4 H), 0.89 (t, J = 6.8 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 204.2, 163.5, 138.5, 138.4, 71.5, 68.3, 64.5, 41.9, 36.9, 31.8, 31.3, 25.4, 22.7, 13.7: HRMS calcd for. C 14 H 18 4 : , Found rel-(2ar,5as,8br)-8-hexyl-4-[(4-methylphenyl)sulfonyl]-2,2a,3,4,5,5a,7,8b-octahy dro-1h-6-oxa-4-azaacenaphthylene-1,7-dione (47). IR (nujol, cm -1 ): 1721(s), 1712(s), 1610(w); 1 H NMR (400 MHz): δ 7.58 (d, J = 8.0 Hz, 2 H), 7.31 (d, J = 8.0 Hz, 2 H), 4.95~5.01 (m, 1 H), 3.98 (dd, J = 18.0, 2.4 Hz, 1 H), 3.77 (dd, J = 10.2, 1.6 Hz, 1 H), 3.47 (t, J = 6.0 Hz, 1 H), 2.90~2.79 (m, 2 H), 2.65~2.61 (m, 1 H), 2.59 (dd, J = 18.4, 7.2 Hz, 1 H), 2.41 (s, 3 H), 2.20 (dd, J = 14.8, 10.4 Hz, 2 H), 1.75 (t, J = 12.2 Hz, 1 H), 1.23~1.13 (m, 8 H), 0.81 (t, J = 16.4 Hz, 3 H); 13 C NMR (100 MHz): δ 203.5, 163.0, 144.4, 138.7, 137.8, 132.7, 130.0, 127.4, 72.6, 47.2, 44.7, 43.4, 37.4, 32.0, 31.3, 29.0, 29.0, 25.5, 22.3, 21.5, 14.0; HRMS Calcd For C 23 H 29 N 5 S: ; Found: (But-3-enyl)-2-((4-fluorophenyl)ethynyl)-2-hexyloxirane (49). IR (neat, cm -1 ): 2965 (w); 1 H NMR (500 MHz, CDCl 3 ): δ 7.38 (dd, 2 H, J = 7.6, 5.0 Hz,), 7.00~6.97 (m, 2 H), 5.90~5.82 (m, 1 H), 5.09 (dd, 1 H, J = 17.2, 1.2 Hz), 4.99 (dd, J = 10.0, 1.2 Hz, 1 H), 2.93 (t, 1 H, J = 7.0 Hz), 2.26~2.21 (m, 2 H), 1.91~1.74 (m, 4 H), 1.68~1.53 (m, 4 H), 1.42~1.33 (m, 4 H), 0.92 (t, 3 H, J = 6.8 Hz); 13 C NMR (125 MHz, CDCl 3 ): δ 163 (d, J CF = Hz), 137.5, (d, 2 x CH, J CF = 8.9 Hz), 118.4, (d, 2 x CH, J CF S21

22 = 21.1 Hz), 115.3, 85.9, 84.0, 64.1, 56.7, 36.9, 31.7, 30.2, 29.5, 29.0, 25.6, 22.5, 14.0; HRMS calcd for C 20 H 25 F: , Found (But-3-enyl)-2-hexyl-2-((4-methoxyphenyl)ethynyl)oxirane (50). IR (neat, cm -1 ): 2970 (w); 1 H NMR (400 MHz, CDCl 3 ): δ 7.36 (d, 2 H, J = 7.2 Hz,), 6.82 (d, 2 H, J = 7.2 Hz,), 5.91~5.82 (m, 1 H), 5.09 (dd, 1 H, J = 16.8, 1.2 Hz), 4.98 (dd, 1 H, J = 11.6, 1.2 Hz), 3.79 (s, 3 H), 2.92 (t, 1 H, J = 6.0 Hz), 2.26~2.22 (m, 2 H), 1.91~1.75 (m, 3 H), 1.69~1.53 (m, 2 H), 1.42~1.33 (m, 7 H), 0.87 (t, 3 H, J = 6.8 Hz); 13 C NMR (100 MHz, CDCl 3 ): δ 159.8, 137.6, (2 x CH), 115.2, 114.5, (2 x CH), 85.0, 84.7, 64.2, 56.9, 55.3, 37.1, 31.7, 30.2, 29.5, 29.0, 25.6, 22.5, 14.0; HRMS calcd for C 21 H 28 2 : , Found (2,2-Dimethyl-but-3-enyl)-2-methyl-2-oct-1-ynyl-oxirane (51). IR (nujol, cm -1 ): 2231(w), 1645(w); 1 H NMR (400 MHz, CDCl 3 ): δ 5.85 (dd, J = 16.0, 12.0 Hz, 1 H), 4.98 (d, J = 8.0 Hz, 1 H), 4.94 (s, 1 H), 2.78 (t, J = 6.0 Hz, 1 H), 2.20 (t, J = 7.2 Hz, 2 H), 1.73 (dd, J = 14.0, 5.6 Hz, 1 H), 1.67 (dd, J = 14.0, 5.6 Hz, 1 H), 1.58~1.20 (m, 11 H), (s. 3 H), (s, 3 H), (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 147.5, 110.8, 85.7, 78.0, 62.4, 52.4, 42.0, 36.0, 31.2, 28.4, 27.0, 26.9, 23.7, 22.5, 18.6, 14.0; Mass (75 ev, m/z): 248 (M + ). 2-methyl-1-[3-methyl-3-(1-octynyl)oxiran-2-yl]-3-butenyl acetate (dr = 1:1) (52). IR (neat, cm -1 ): 2240(w), 1723(s), 1631(w); 1 H NMR (400 MHz, CDCl 3 ): for isomer one δ 5.93~5.77 (m, 1 H), 5.12~5.05 (m, 2 H), 4.93~4.88 (m, 1 H), 2.89 (d, 1 H, J = 8.4 Hz), 2.62 (quin, 1 H, J = 7.2 Hz), 2.22 (t, 2 H, J = 6.8 Hz), 2.09 (s, 3 H), 1.51 (s, 3 H), 1.53~1.42 (m, 2 H), 1.40~1.15 (m, 4 H), 1.08 (d, 3 H, J = 7.2 Hz), 0.90 (t, 3 H, J = 6.4 Hz), for another isomer δ 2.87 (d, 1 H, J = 8.4 Hz), 2.07 (s, 3 H), 1.48 (s, 3 H), 1.07 (d, 3 H, J = 7.2 Hz), rest of the peak merged with isomer one; 13 C NMR (100 MHz, CDCl 3 ): δ 169.7, 138.7, 138.2, 115.6, 115.4, 86.5, 86.4, 77.0, 76.9, 76.0, 63.8, 63.6, 52.9, 52.3, 40.5, 40.3, 31.0, 28.3, 28.1, 23.5, 23.3, 22.3, 20.7, 18.4, 15.8, 15.3, S22

23 HRMS calcd. for C 18 H 28 3 : , found rel-(1ar,3ar,6br)-6b-methyl-6-(1,1,1-trimethylsilyl)-1a,2,3,3a,5,6b-hexahydro-1 H-4-oxacyclobuta[cd]inden-5-one (53). IR (nujol, cm -1 ): 1714(s), 1612(w); 1 H NMR (400 MHz): δ 4.48 (t, J = 8.4 Hz, 1 H), 3.51 (dd, J = 12.4, 9.6 Hz, 1 H), 2.65 (dd, J = 15.6, 1.6 Hz, 1 H), 2.47 (t, J = 8.6 Hz, 1 H), 2.10~2.17 (m, 2 H), 1.81~1.90 (m, 1 H), 1.72~1.77 (m, 1 H), 1.38 (s, 3 H), (s, 9 H); 13 C NMR (100 MHz): δ 174.2, 128.6, 124.1, 86.0, 53.2, 40.4, 39.7, 31.41, 29.8, 17.6, (3 CH 3 ); HRMS Calcd For C 13 H 20 2 Si: ; Found: rel-(1ar,3ar,6br)-6-[3-(1,3-dioxolan-2-yl)propyl]-6b-methyl-1a,2,3,3a,5,6b-hexa hydro-1h-4-oxacyclobuta[cd]inden-5-one (54). IR (neat, cm -1 ): 1712 (w); 1 H NMR (500 MHz, CDCl 3 ): δ 4.83 (t, J = 4.5 Hz, 1H), 4.49 (t, J = 8.0 Hz, 1H), 3.93 (t, J = 7.2 Hz, 2H), 3.82 (t, J = 7.2 Hz, 2H), 3.36 (q, J = 8.0 Hz, 1H), 2.57 (d, J = 12 Hz, 1H), 2.46 (t, J = 8.8 Hz, 1H), 2.29~2.15 (m, 4H), 1.88 (m, 1H), 1.76 (m, 1H), 1.68~1.57 (m, 4H), 1.38 (s, 3H); 13 C NMR (125 MHz, CDCl 3 ): δ 163.7, 157.2, 123.0, 104.2, 86.7, 64.8, 52.1, 40.2, 37.4, 33.7, 32.1, 27.7, 26.9, 22.6, 17.8; MS (75 ev, m/z): 278 (M + ); HRMS calcd for C 16 H 22 4 : , Found rel-(1ar,3ar,6br)-6-butyl-6b-ethyl-1a,2,3,3a,5,6b-hexahydro-1h-4-oxacyclobuta [cd]inden-5-one (55). IR (neat, cm -1 ): 1715(s), 1612(w); 1 H NMR (500 MHz, CDCl 3 ): δ 4.54 (t, 1 H, J = 8.0 Hz), 3.32 (dd, 1 H, J = 15.2, 9.6 Hz), 2.54~2.49 (m, 2 H), 2.23~2.07 (m, 4 H), 1.84~1.65 (m, 4 H), 1.38 (quin, 2 H, J = 6.8 Hz), 1.27 (quin, 2 H, J = 6.8 Hz), 0.93 (t, 3 H, J = 7.2 Hz), 0.84 (t, 3 H, J = 7.2 Hz); 13 C NMR (125 MHz, CDCl 3 ): δ 163.8, 155.5, 124.0, 84.4, 56.6, 38.1, 37.9, 32.2, 30.1, 27.8, 26.8, 24.6, 22.5, 13.6, 9.1; HRMS calcd. For C 15 H 22 2 : , found rel-(1ar,3ar,6br)-6,6b-dihexyl-1a,2,3,3a,5,6b-hexahydro-1h-4-oxacyclobuta[cd] inden-5-one (56). IR (neat, cm -1 ): 1705 (s); 1 H NMR(CDCl 3, 400MHz): δ 4.54 (t, J = 8.4 Hz, 1H), 3.25 (q, J = 9.0 Hz, 1H), 2.52 (m, 2H), 2.22~2.08 (m, 6H), 1.81~1.65 (m, S23

24 8H), 1.42~1.26 ( m, 10H),, 0.82 (t, J = 6.8 Hz, 6H); 13 C NMR(CDCl 3, 100MHz): δ 163.9, 155.8, 124.0, 84.8, 56.1, 38.6, 38.0, 32.1, 32.0, 31.6, 31.4, 29.6, 29.1, 27.9, 27.1, 24.9, 22.5, 13.9; MS (75 ev, m/z): 318 (M + ); HRMS calcd for C 21 H 34 2 : , Found rel-(1ar,3ar,6br)-6b-hexyl-6-phenyl-1a,2,3,3a,5,6b-hexahydro-1h-4-oxacyclobu ta[cd]inden-5-one (57). IR (neat, cm -1 ): 1716 (s); 1 H NMR(CDCl 3, 400MHz): δ 7.30~7.25 (m, 2H), 7.23~7.19 (m, 3H), 4.62 (t, J = 8.4 Hz, 1H), 3.59 (q, J = 9.0 Hz, 1H), 2.61 (t, J = 6.6 Hz, 1H), 2.53 (dd, J = 15.6, 2.4 Hz, 1H), 2.20~2.12 (m, 2H), 1.83~1.66 (m, 4H), 1.42~1.22 ( m, 8H),, 0.82 (t, J = 6.8 Hz, 3H); 13 C NMR(CDCl 3, 100MHz): δ 162.8, 157.8, 132.6, 128.4, 128.3, 127.9, 125.5, 84.4, 57.3, 40.8, 39.4, 32.0, 31.8, 31.7, 29.7, 27.7, 25.1, 22.6, 14.0; MS (75 ev, m/z): 310 (M + ); HRMS calcd for C 21 H 26 2 : , Found rel-(1ar,3ar,6br)-6-(4-fluorophenyl)-6b-hexyl-1a,2,3,3a,5,6b-hexahydro-1h-4-o xacyclobuta[cd]inden-5-one (58). IR (neat, cm -1 ): 1715 (s); 1 H NMR(CDCl 3, 500MHz): δ 7.30~7.26 (m, 2 H), 7.03 (t, 2 H, J = 8.5 Hz), 4.67 (t, 1 H, J = 8.5 Hz,), 3.59 (dd, 1 H, J = 16.0, 9.5 Hz), 2.67 (t, 1 H, J = 8.0 Hz), 2.56 (dd, 1H, J = 16.0 Hz), 2.29~2.12 (m, 2 H), 1.89~1.70 (m, 4 H), 1.48~1.22 ( m, 8 H),, 0.87 (t, 3 H, J = 6.8 Hz); 13 C NMR(CDCl 3, 125 MHz): δ 162.7, (d, J CF = Hz), 157.6, 130.1, (d, 2 x CH, J CF = 8.9 Hz), 128.6, 124.6, (d, 2 x CH, J CF = 21.1 Hz), 84.4, 57.2, 40.7, 39.5, 32.0, 31.9, 31.7, 29.7, 27.7, 25.1, 22.6, 14.0; HRMS calcd for C 21 H 25 F 2 : , Found rel-(1ar,3ar,6br)-6b-hexyl-6-(4-methoxyphenyl)-1a,2,3,3a,5,6b-hexahydro-1h-4 -oxacyclobuta[cd]inden-5-one (59). IR (neat, cm -1 ): 1722 (s); 1 H NMR (CDCl 3, 500MHz): δ 7.26 (d, 2 H, J = 8.4 Hz), 6.88 (d, 2 H, J = 8.0 Hz), 4.66 (t, 1 H, J = 8.5 Hz,), 3.80 (s, 3 H), 3.62 (dd, 1 H, J = 16.0, 9.5 Hz), 2.65 (t, 1 H, J = 8.0 Hz), 2.56 (dd, 1H, J = 16.0 Hz), 2.29~2.16 (m, 4 H), 1.89~1.69 (m, 3 H), 1.48~1.08 ( m, 7 H),, 0.88 S24

25 (t, 3 H, J = 6.8 Hz); 13 C NMR(CDCl 3, 125 MHz): δ 162.9, 159.3, 155.4, (2 x CH), 125.2, 125.0, (2 x CH), 84.4, 57.1, 55.3, 40.7, 39.4, 32.1, 31.9, 31.7, 29.7, 27.8, 25.1, 22.6, 14.0; HRMS calcd for C 22 H 28 3 : , Found rel-(4as,7ar,7br)-3-hexyl-6,6,7b-trimethyl-2,4,4a,5,6,7,7a,7b-octahydrocyclobut a[de]chromen-2-one (60). IR (nujol, cm -1 ): 1715(s), 1611(w); 1 H NMR (400 MHz, CDCl 3 ): δ 4.52 (t, J = 8.0 Hz, 1 H), 3.20 (dd, J = 15.2, 9.6 Hz, 1 H), 2.76 (d, J = 16.0 Hz, 1 H), 2.29~2.22 (m, 1 H), 2.14 (dd, J = 14.8, 7.6 Hz, 1 H), 2.06 (dd, J = 16.0, 8.4 Hz, 1 H), 1.95 (dd, J = 13.2, 8.4 Hz, 1 H), 1.43~1.35 (m, 5 H), 1.26~1.18 (m, 6 H), 1.00 (s, 3 H), (s, 3 H), (t, J = 6.8 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 164.3, 156.3, 123.6, 85.0, 52.2, 51.1, 45.3, 38.8, 33.0, 31.7, 29.6, 28.2, 27.2, 26.1, 22.8, 19.2, 14.2; HRMS calcd. for C 18 H 28 2 : , Found: rel-(1as,3s,3as,6br)-6-hexyl-6b-methyl-5-oxo-1a,2,3,3a,5,6b-hexahydro-1h-4-ox acyclobuta[cd]inden-3-yl acetate (61). IR (nujol, cm -1 ): 1723(s), 1713(s), 1615(w); 1 H NMR (400 MHz, CDCl 3 ): 5.51~5.45 (q, J = 8.0 Hz, 1 H), 4.44 (d, J = 6.0 Hz, 1 H), 3.38 (dd, J = 15.2, 9.2 Hz, 1 H), 2.64 (d, J = 14.8, 1 H), 2.60 (d, J = 9.2, 1 H), 2.39 (dd, J = 14.4, 8.0 Hz, 1 H), 2.24~2.14 (m, 2 H), 2.02 (s, 3 H), 1.87~1.83 (m, 1 H), 1.46~1.26 (m, 11 H), (t, J = 7.2 Hz, 3 H); 13 C NMR (100MHz, CDCl 3 ): , 162.9, 155.9, 124.5, 89.5, 80.0, 49.3, 38.6, 37.8, 34.5, 31.4, 29.1, 27.8, 27.1, 22.5, 20.8, 17.7, 14.0; HRMS calcd. for C 18 H 26 4 : , Found: rel-(1as,2s,3s,3as,6br)-6-hexyl-2,6b-dimethyl-5-oxo-1a,2,3,3a,5,6b-hexahydro-1 H-4-oxacyclobuta[cd]inden-3-yl acetate (62a). C 6 H 13 H 1 Ac H 2 Me a Me b H 3 62a H 4 H 6 H 5 Irradiation Increase (%) Me b (δ 0.79) H 1 δ 4.48 (0.76%) H 3 δ 2.27 (1.43%) H 4 δ 2.51 (1.71%) Me a (δ 1.40) H 1 δ 4.48 (0.88%) H 4 δ 2.51 (0.54%) H 5 δ 3.40 (0.37%) S25

26 IR (neat, cm -1 ): 1732(s), 1705(w) 1042 (s); 1 H NMR (400 MHz, CDCl 3 ): δ 5.46 (t, 1 H, J = 7.2 Hz), 4.48 (d, 1 H, J = 7.2 Hz), 3.40 (dd, 1 H, J = 15.2, 9.6 Hz), 2.70 (d, 1 H, J = 15.2 Hz), 2.51 (quin, 1 H, J = 7.2 Hz), 2.27 (d, 1 H, J = 8.0 Hz), 2.22~2.14 (m, 2 H), 2.10 (s, 3 H), 1.40 (s, 3 H), 1.45~1.38 (m, 1 H), 1.29~1.20 (m, 7 H), 0.84 (t, 3 H, J = 6.0 Hz), 0.79 (d, 3 H, J = 7.2 Hz); 13 C NMR (100 MHz, CDCl 3 ): δ 170.3, 163.0, 156.5, 124.5, 88.2, 80.8, 47.2, 47.0, 38.3, 37.0, 31.4, 29.2, 27.8, 27.3, 22.5, 20.6, 18.7, 16.3, 14.0; HRMS calcd. for C 19 H 28 4 : , found rel-(1as,2r,3s,3as,6br)-6-hexyl-2,6b-dimethyl-5-oxo-1a,2,3,3a,5,6b-hexahydro-1 H-4-oxacyclobuta[cd]inden-3-yl acetate (62b). C 6 H 13 H 1 Ac H 2 Me a H 3 Me b 62b H 4 H 6 H 5 Irradiation Increase (%) Me b (δ 0.99) H 2 δ 5.45 (0.78%) H 6 δ 2.86 (1.04%) Me a (δ 1.36) H 1 δ 4.31 (1.03%) H 4 δ 2.51 (0.79%) IR (neat, cm -1 ): 1735(s), 1703(w) 1038 (s); 1 H NMR (400 MHz, CDCl 3 ): δ 5.45 (dd, 1 H, J = 10.4, 6.4 Hz), 4.31 (d, 1 H, J = 6.4 Hz), 3.18 (dd, 1 H, J = 15.6, 9.6 Hz), 2.86 (dd, 1 H, J = 15.6, 2.0 Hz), 2.51 (t, 1 H, J = 7.2 Hz), 2.28~2.10 (m, 3 H), 2.02 (s, 3 H), 1.36 (s, 3 H), 1.49~1.20 (m, 8 H), 0.99 (d, 3 H, J = 6.4 Hz), 0.82 (t, 3 H, J = 6.8 Hz); 13 C NMR (100 MHz, CDCl 3 ): δ 107.2, 163.0, 156.0, 124.2, 88.7, 82.6, 48.4, 42.4, 38.2, 31.7, 31.4, 29.3, 27.8, 27.1, 22.5, 20.9, 18.0, 14.3,14.0; HRMS calcd. for C 19 H 28 4 : , found [(3E)-5-Methyl-3,5-hexadienyl]-3-(1-octynyl)oxirane (E :Z = 9:1) (65). 1 H NMR (400 MHz, CDCl 3 ): δ 6.18 (d, 1 H, J = 16.4 Hz), 5.68 (dt, 1 H, J = 16.4, 7.6 Hz), 4.86 (s, 2 H), 3.40 (dt, 1 H, J = 3.6, 1.6 Hz), 2.98 (td, 1 H, J = 6.4, 3.6 Hz), 2.33~2.27 (m, 2 H), 2.20 (td, 2 H, J = 7.2, 1.6 Hz), 1.88~1.72 (m, 2 H), 1.82 (s, 3 H), 1.52~1.44 (m, 2 H), 1.39~1.24 (m, 6 H), 0.86 (t, 3 H, J = 6.8 Hz); 13 C NMR (100 MHz, CDCl 3 ): δ 141.8, S26