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, 30043 ------------ E-mail: rsliu@mx.nthu.edu.tw Contents: (1) Representative synthetic procedures for cis-epoxy ene-ynes. Synthesis of cis-epoxyenynes 7, 14 and 20------------------------------------------------------ S1 (2) Spectral data for compounds 1-68 ------------------------------------------------ S5 S1
(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
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 13 14 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
(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 13 20 13 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
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), 0.884 (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), 0.848 (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
(m, 4 H), 1.25 (s, 3 H), 0.879 (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 : 228.1352, Found: 228.1358. 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: 485.2236, Found: 485.2232. 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: 467.2130, Found: 467.2133. 3-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
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 : 268.1094; Found: 268.1099. 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 : 240.1175 ; Found: 240.1177. 3-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), 1.80-1.74 (m, 2 H) 1.48 (s, 3 H), 1.48-1.22 (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, 276.1716, Found 276.1718 S7
2, -0.29 (3 CH 3 ); HRMS Calcd For C 14 H 20 2 Si: 264.1230 ; Found: 264.1235. 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, 248.1780, Found, 248.1783 2-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 1137.2, 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, 254.0948, Found 254.0950 3-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 5.85-5.94 (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
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), 1.36-1.15 (m, 8 H), 0.850 (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 : 292.1675, Found 292.1670. NE-map of Compound 7a: H 1 nc 6 H 13 20 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, 13.9. HRMS calcd. for C 15 H 24 2 : 236.1776, found 236.1775. (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
(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), 0.130 (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, -0.39 (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 : 250.1569, Found 250.1566 3-(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 : 206.1671, found 206.1665. 3-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 : 290.2610, Found 290.2606. S10
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 : 282.1984, Found 282.1981. 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), 0.869 (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), 0.859 (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
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 : 264.1725, found 264.1720. 3-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 : 208.1463, Found 208.1463. 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
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: 361.1712, Found 361.1711. 2-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), 0.868 (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), 0.857 (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 5.93-5.81 (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), 0.870 (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
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: 222.1440, Found 222.1436. 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), 0.878 (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 : 278.1882, found 278.1876. 2-Allyloxymethyl-3-hex-1-ynyl-oxirane (26). IR (neat, cm -1 ): 2230(w), 1641(w); 1 H NMR (400 MHz, CDCl 3 ): δ 5.5.96~5.81 (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
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 : 306.1467, Found 306.1465. 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
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 : 262.1569, found 262.1563. 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 : 346.2508, Found 346.2506. 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 : 338.1882, Found 338.1880. 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
1.42~1.27 (m, 11 H), 0.866 (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, 7.84. Found, C, 68.02, H, 7.66. 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), 0.868 (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 : 306.1831, Found: 306.1829. 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 : 320.1624, found 320.1613. 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
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 : 264.1362, Found 264.1359. 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: 445.1930 ; Found: 445.1932. NE-map of Compound 38: H 1 nc 6 H 13 21 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, 127.50, 78.6, 48.7, 46.1, 41.0, 40.3, 38.4, 31.2, 25.1, 24.8, S18
22.4, 21.5, 13.7; HRMS calcd. for C 22 H 27 N 5 S: 417.1610, Found: 417.1606. 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), 0.848 (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 : 406.1992, Found: 406.1988. NE-map of compound 40. H 1 nc 6 H 13 19 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), 0.844 (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 : 392.1835, Found: 392.1837. 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
9 H), 0.830 (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 : 262.1569, Found 262.1566. 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: 292.1495, Found 292.1492. 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), 0.851 (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 : 320.1624, Found: 320.1628. 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 : 334.1780, found S20
334.1785. 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 : 250.1214, Found 250.1217. 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: 431.1763 ; Found: 431.1769. 3-(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 = 248.4 Hz), 137.5, 133.8 (d, 2 x CH, J CF = 8.9 Hz), 118.4, 115.5 (d, 2 x CH, J CF S21
= 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: 300.1889, Found 300.1884. 3-(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, 133.3 (2 x CH), 115.2, 114.5, 113.9 (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 : 312.2089, Found 312.2093. 3-(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), 0.991 (s. 3 H), 0.980 (s, 3 H), 0.875 (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, 13.8. S22
HRMS calcd. for C 18 H 28 3 : 292.2038, found 292.2033. 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), 0.180 (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, -0.86 (3 CH 3 ); HRMS Calcd For C 13 H 20 2 Si: 236.1231 ; Found: 236.1235. 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 : 278.1518, Found 278.1514. 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 : 234.1620, found 234.1630. 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
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 : 318.2559, Found 318.2553. 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 : 310.1933, Found 310.1931. 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, 162.3 (d, J CF = 247.2 Hz), 157.6, 130.1, (d, 2 x CH, J CF = 8.9 Hz), 128.6, 124.6, 115.4 (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 : 328.1839, Found 328.1843. 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
(t, 3 H, J = 6.8 Hz); 13 C NMR(CDCl 3, 125 MHz): δ 162.9, 159.3, 155.4, 129.6 (2 x CH), 125.2, 125.0, 113.8 (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 : 340.2038, Found 340.2032. 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), 0.915 (s, 3 H), 0.858 (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 : 276.2089, Found: 276.2085. 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), 0.863 (t, J = 7.2 Hz, 3 H); 13 C NMR (100MHz, CDCl 3 ): 170.32, 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 : 306.1831, Found: 306.1835. 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
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 : 320.1988, found 320.1987. 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 : 320.1988, found 320.1987. 2-[(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