S1
An oxidative Hosomi-Sakurai strategy toward the synthesis of illioliganones B and C Wesley J. Moran,* and Arantxa Rodríguez
Department of Chemical & Biological Sciences, University of Huddersfield, Huddersfield HD1
3DH (UK)
E-mail: [email protected]
Contents
General experimental information S2
Experimental procedures S2
Copies of NMR spectra S8
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S2
General. 1H NMR spectra were recorded at 400 or 500 MHz. 13C NMR spectra were recorded at
100 or 125 MHz. Chemical shifts are reported in ppm from tetramethylsilane with the solvent
resonance as the internal standard (CDCl3: 7.26 ppm). Data are reported as follows: chemical shift,
integration, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, br = broad, m = multiplet),
and coupling constants (Hz). 13C NMR were recorded with complete proton decoupling. Chemical
shifts are reported in ppm from tetramethylsilane with the solvent as the internal standard (CDCl3:
77.4 ppm). Mass spectrometry (m/z) was performed in ESI mode, with only molecular ions being
reported. Infrared (IR) spectra νmax are reported in cm-1. Bands are characterised as broad (br),
strong (s), medium (m) and weak (w). All purchased reagents were used as received without further
purification. THF was pre-dried with 3A molecular sieves then distilled from sodium benzophenone
ketyl. Petroleum ether refers to the fraction boiling at 40-60 oC. Isobutyl 2-methylbut-3-en-2-yl
carbonate was prepared according to a literature method.1
Synthesis of 6-(3-methylbut-2-enyl)benzo[d][1,3]dioxol-5-ol, 3
Isobutyl 2-methylbut-3-en-2-yl carbonate (3.28 g, 18 mmol, 1.3 equiv) and sesamol (1.87 g, 14 mmol, 1 equiv) were dissolved in THF (50 mL) at room temperature under a nitrogen atmosphere. Tetrakistriphenylphosphine palladium(0) (162 mg, 0.14 mmol, 0.01 equiv) was added in one portion and the mixture was stirred for 15h. The reaction mixture was concentrated, then diluted with 20:1 petroleum ether/ethyl acetate and filtered through celite to remove the palladium salts. The resulting solution was concentrated and then heated neat at 125 oC for 3 h. The mixture was purified by flash chromatography on silica gel using 20:1 petroleum ether/ethyl acetate to furnish 3 as a colourless oil (2.6 g, 90%). IR (neat): 1036 (s), 1164 (s), 1439 (m), 1481 (m), 1503 (m), 3452 (br) cm-1. 1H NMR (400 MHz, CDCl3): δ 1.76 (6H, s), 3.24 (2H, d, J = 7.2 Hz), 4.96 (1H, s), 5.22-5.29 (1H,
m), 5.86 (2H, s), 6.41 (1H, s), 6.57 (1H, s).
13C NMR (100 MHz, CDCl3): δ 18.2, 26.2, 30.0, 98.9, 101.3, 109.5, 118.8, 122.2, 135.3, 141.6,
146.7, 149.1.
MS: m/z (M-1) 205.1 HRMS: m/z calc’d for C12H13O3 205.0870, found 205.0867.
1 B. Plietker, A. Dieskau, K. Möws and A. Jatsch, Angew. Chem., Int. Ed. 2008, 47, 198.
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Synthesis of trimethyl(6-(3-methylbut-2-enyl)benzo[d][1,3]dioxol-5-yloxy)silane, 6
6-(3-Methylbut-2-enyl)benzo[d][1,3]dioxol-5-ol (270 mg, 1.3 mmol, 1 equiv), 3, was dissolved in THF (2.4 mL) at room temperature under a nitrogen atmosphere. Triethylamine (0.49 mL, 3.5 mmol, 2.4 equiv), followed by chlorotrimethylsilane (0.48 mL, 3.8 mmol, 2.6 equiv), was added slowly to the reaction mixture. After 1 h, the crude mixture was filtered through celite, washed through with petroleum ether, and concentrated. If any triethylaminehydrochloride salt remained, 20:1 petroleum ether/ethyl acetate was added to the sample which was then filtered again and concentrated. The product, 6, was isolated as a clear pale yellow oil (370 mg, 100%) which was taken through to the next step without further purification. IR (neat): 1157 (s), 1182 (s), 1479 (s), 2962 (w) cm-1. 1H NMR (400 MHz, CDCl3): δ 0.26 (9H, s), 1.70 (3H, s), 1.74 (3H, s), 3.19 (2H, d, J = 7.3 Hz),
5.19-5.29 (1H, m), 5.87 (2H, s), 6.38 (1H, s), 6.62 (1H, s).
13C NMR (100 MHz, CDCl3): δ 0.72, 18.1, 26.1, 28.7, 101.2, 101.7, 109.3, 123.3, 124.7, 132.7,
142.0, 145.9, 147.3.
MS: unable to obtain MS data because of lability of O-Si bond.
Procedure for the oxidative Hosomi-Sakurai reaction
Trimethyl(6-(3-methylbut-2-enyl)benzo[d][1,3]dioxol-5-yloxy)silane, 6 (45 mg, 0.16 mmol, 1 equiv) was dissolved in trifluoroethanol (1 mL) at room temperature and stirred open to air. Sodium bicarbonate (40 mg, 0.48 mmol, 3 equiv) was added, followed by allyltrimethylsilane (0.039 mL, 0.24 mmol, 1.5 equiv). Iodobenzene diacetate (77 mg, 0.24 mmol, 1.5 equiv) was dissolved in trifluoroethanol (0.5 mL) and added over 10 seconds to the reaction mixture. After stirring the dark red solution for about 1 hour, saturated aqueous sodium bicarbonate solution was added and the mixture was extracted with ethyl acetate. This was dried over MgSO4, filtered, concentrated, then purified by flash chromatography on silica gel with 20:1 to 5:1 petroleum ether/ethyl acetate to furnish three compounds as colourless oils (2: 15 mg, 38%; 1: 3 mg, 8%, 7: 10 mg, 21%).
Data for 6-allyl-6-(3-methylbut-2-enyl)benzo[d][1,3]dioxol-5(6H)-one, 2
IR (neat): 1219 (s), 1385 (s), 1626 (s) cm-1.
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1H NMR (400 MHz, CDCl3): δ 1.57 (3H, s), 1.62 (3H, s), 2.14-2.28 (2H, m), 2.51 (1H, dd, J = 14,
7.4 Hz), 2.59 (1H, dd, J = 14, 7.2 Hz), 4.86-5.04 (3H, m), 5.41 (1H, s), 5.47-5.62 (1H, m), 5.60 (1H,
s), 5.80 (1H, s), 5.81 (1H, s).
13C NMR (100 MHz, CDCl3): δ 18.4, 26.3, 39.6, 45.1, 54.4, 99.9, 101.6, 109.1, 118.4, 118.7, 133.5,
135.3, 144.3, 164.4, 202.8.
MS: m/z (M+23) 269.1 HRMS: m/z calc’d for C15H18NaO3 269.1148, found 269.1136. Data for 7a-allyl-6-(3-methylbut-2-enyl)benzo[d][1,3]dioxol-5(7aH)-one, 1 IR (neat): 1175 (s), 1621 (s), 1676 (m), 2913 (w) cm-1. 1H NMR (400 MHz, CDCl3): δ 1.60 (3H, s), 1.74 (3H, s), 2.38 (1H, dd, J = 14, 7.6 Hz), 2.60 (1H,
dd, J = 14, 7.1 Hz), 2.94 (1H, dd, J = 17, 7.3 Hz), 3.03 (1H, dd, J = 17, 7.3 Hz), 5.02-5.18 (3H, m),
5.55 (1H, s), 5.56-5.68 (1H, m), 5.58 (1H, s), 5.62 (1H, s), 6.56 (1H, t, J = 1.7 Hz).
13C NMR (100 MHz, CDCl3): δ 18.0, 26.1, 27.9, 40.9, 81.4, 98.3, 98.9, 120.3, 121.2, 130.5, 133.9,
135.2, 140.7, 173.9, 187.9.
MS: m/z (M+23) 269.1 HRMS: m/z calc’d for C15H18NaO3 269.1148, found 269.1159. Data for 6-(3-methylbut-2-enyl)-7a-(2,2,2-trifluoroethoxy)benzo[d][1,3]dioxol-5(7aH)-one, 7 IR (neat): 1103 (s), 1123 (s), 1268 (m), 1280 (m), 1635 (m), 1654 (m), 1690 (m) cm-1. 1H NMR (400 MHz, CDCl3): δ 1.61 (3H, s), 1.76 (3H, s), 2.99 (1H, dd, J = 18, 7.3 Hz), 3.09 (1H,
dd, J = 18, 7.3 Hz), 3.72-3.95 (2H, m), 5.09-5.17 (1H, m), 5.63 (1H, s), 5.63 (1H, s), 5.67 (1H, s),
6.52 (1H, t, J = 1.8 Hz).
13C NMR (100 MHz, CDCl3): δ 18.0, 26.1, 28.1, 98.2, 99.4, 99.9, 119.2, 122.2, 125.0, 125.6, 136.3,
144.7, 167.1, 186.8.
MS: m/z (M+23) 327.1 HRMS: m/z calc’d for C14H15F3NaO4 327.0815, found 327.0814.
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Synthesis of illioliganone C by Upjohn dihydroxylation
6-Allyl-6-(3-methylbut-2-enyl)benzo[d][1,3]dioxol-5(6H)-one, 2, (160 mg, 0.65 mmol, 1 equiv) was dissolved in acetone (0.3 mL), water (0.72 mL) and t-butanol (0.3 mL) at room temperature. N-Methylmorpholine N-oxide (132 mg, 0.98 mmol, 1.5 equiv) was added to the reaction mixture followed by osmium tetroxide (8 mg, 0.031 mmol, 0.05 equiv). After stirring for 3h, water was added and the mixture extracted with ethyl acetate. The organic layer was separated, dried over MgSO4, filtered and concentrated. Purification by flash chromatography on silica gel using 2:1 petroleum ether/ethyl acetate was undertaken two times and illioliganone C was isolated. IR (neat): 1221 (s), 1385 (s), 1626 (s) cm-1. 1H NMR (500 MHz, acetone-d6): δ 1.06 (6H, s), 1.83 (1H, dd, J = 13.7, 1.8 Hz), 2.04-2.10 (1H, m),
2.24 (1H, dd, J = 13.0, 7.5 Hz), 2.48 (1H, dd, J = 13.1, 7.1 Hz), 3.06 (1H, d, J = 6.4 Hz), 3.29 (1H,
s), 3.34 (1H, ddd, J = 10.7, 6.4, 1.9 Hz), 4.87-5.00 (2H, m), 5.46 (1H, s), 5.52-5.64 (1H, m), 5.54
(1H, s), 5.88 (1H, s), 5.90 (1H, s).
Literature values:2 (400 MHz, acetone-d6): δ 1.07 (s), 1.82 (dd, J = 13.6, 2.0 Hz), 2.10 (d, J = 13.6
Hz), 2.24 (dd, J = 13.2, 7.2 Hz), 2.48 (dd, J = 13.2, 7.2 Hz), 3.05 (d, J = 6.0 Hz), 3.27 (s), 3.33 (m),
4.91 (dd, J = 10.0, 2.0 Hz), 4.96 (dd, J = 16.8, 2.0 Hz), 5.46 (s), 5.54 (s), 5.57 (m), 5.88 (s), 5.89 (s).
13C NMR (125 MHz, acetone-d6): δ 25.4, 25.7, 43.3, 46.9, 52.4, 72.6, 76.6, 99.7, 102.4, 108.4,
118.0, 134.3, 145.1, 163.8, 202.0.
Literature values: (100 MHz, acetone-d6): δ 25.4, 25.7, 43.3, 46.9, 52.3, 72.6, 76.3, 99.6, 102.3,
108.3, 117.9, 134.2, 145.1, 163.8, 202.1.
MS: m/z (M+23) 303.1 HRMS: m/z calc’d for C15H20NaO5 303.1203, found 303.1203
2 W.-Z. Tang, S.-G. Ma, S.-S. Yu, J. Qu, Y.-B. Liu and J. Liu, J. Nat. Prod., 2009, 72, 1017.
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Synthesis of 6-allyl-6-((3,3-dimethyloxiran-2-yl)methyl)benzo[d][1,3]dioxol-5(6H)-one, 12
6-Allyl-6-(3-methylbut-2-enyl)benzo[d][1,3]dioxol-5(6H)-one, 2, (45 mg, 0.16 mmol, 1 equiv) was dissolved in CH2Cl2 (2 mL) at room temperature and m-chloroperbenzoic acid (70%, 36 mg, 0.21 mmol, 1.3 equiv) was added. After stirring for 5 h, the reaction mixture was quenched with saturated aqueous sodium thiosulfate solution and extracted with CH2Cl2. The organic layer was dried over MgSO4, filtered and concentrated. Purification by flash chromatography on silica gel using 20:1 petroleum ether/ethyl acetate furnished 12 as a colourless oil (29 mg, 70%). IR (neat): 1221 (s), 1385 (s), 1626 (s), 1720 (w) cm-1. 1H NMR (400 MHz, CDCl3): δ 1.18 (3H, s), 1.20 (3H, s), 1.56 (1H, dd, J = 14, 7.3 Hz), 2.25 (1H,
dd, J = 13, 7.5 Hz), 2.35 (1H, dd, J = 14, 3.8 Hz), 2.42 (1H, dd, J = 7.3, 3.8 Hz), 2.56 (1H, dd, J =
13, 7.3 Hz), 4.94-5.06 (2H, m), 5.48-5.61 (1H, m), 5.53 (1H, s), 5.67 (1H, s), 5.82 (1H, s), 5.84 (1H,
s).
13C NMR (100 MHz, CDCl3): δ 19.2, 25.0, 40.4, 46.4, 53.3, 58.1, 61.3, 99.8, 102.0, 109.0, 119.1,
132.5, 144.3, 165.1, 202.4.
MS: m/z (M+23) 285.1 HRMS: m/z calc’d for C15H18NaO4 285.1097, found 285.1093.
Synthesis of 6-allyl-6-(2,3-dihydroxy-3-methylbutyl)benzo[d][1,3]dioxol-5(6H)-one, 11
A mixture of 6-allyl-6-((3,3-dimethyloxiran-2-yl)methyl)benzo[d][1,3]dioxol-5(6H)-one, 12 (49 mg, 0.19 mmol) and water (1.5 mL) was heated at 60 oC overnight. Upon cooling, the mixture was extracted with ethyl acetate, dried over MgSO4, filtered and concentrated. Purification by flash chromatography on silica gel using 1:1 to 1:2 petroleum ether/ethyl acetate furnished 11 as a colourless oil (42 mg, 79%).
IR (neat): 1221 (s), 1385 (s), 1626 (s) cm-1.
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1H NMR (400 MHz, acetone-d6): δ 1.03 (3H, s), 1.05 (3H, s), 1.55 (1H, dd, J = 14, 9.4 Hz), 2.19
(1H, d, J = 14 Hz), 2.31 (1H, dd, J = 13, 7.4 Hz), 2.50 (1H, dd, J = 13, 7.2 Hz), 3.00-3.10 (1H, m),
3.42 (1H, br), 3.63 (1H, d, J = 5.0 Hz), 4.88-5.03 (2H, m), 5.52 (1H, s), 5.52-5.64 (1H, m), 5.68
(1H, s), 5.91 (1H, s), 5.94 (1H, s).
13C NMR (100 MHz, acetone-d6): δ 23.6, 24.8, 42.9, 46.1, 53.0, 72.0, 75.6, 98.4, 101.9, 110.1,
117.2, 133.3, 142.8, 164.9, 201.6.
MS: m/z (M+23) 303.1 HRMS: m/z calc’d for C15H20NaO5 303.1203, found 303.1203.
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NMR spectra for 6-(3-methylbut-2-enyl)benzo[d][1,3]dioxol-5-ol, 3
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5 ppm
1.75
761.
7605
3.23
123.
2493
4.96
285.
2556
5.86
46
6.40
726.
5747
6.11
2.03
1.02
1.01
2.03
1.00
1.00
Current Data ParametersNAME WM-322EXPNO 5PROCNO 1
F2 - Acquisition ParametersDate_ 20100420Time 13.53INSTRUM dpx400PROBHD 5 mm QNP 1H/1PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 8278.146 HzFIDRES 0.126314 HzAQ 3.9584243 secRG 181DW 60.400 usecDE 6.00 usecTE 289.9 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 8.40 usecPL1 -3.00 dBSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300118 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
2030405060708090100110120130140150160170180190 ppm
18.2
107
26.1
592
30.0
164
98.8
534
101.
2540
109.
5173
118.
7945
122.
1939
135.
3100
141.
5801
146.
7115
149.
0861
Current Data ParametersNAME WM-322EXPNO 6PROCNO 1
F2 - Acquisition ParametersDate_ 20100420Time 13.55INSTRUM dpx400PROBHD 5 mm QNP 1H/1PULPROG zgpg30TD 65536SOLVENT CDCl3NS 256DS 4SWH 23980.814 HzFIDRES 0.365918 HzAQ 1.3664756 secRG 18390.4DW 20.850 usecDE 6.00 usecTE 290.1 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 8
======== CHANNEL f1 ========NUC1 13CP1 9.70 usecPL1 -3.00 dBSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 84.00 usecPL2 -3.00 dBPL12 18.00 dBPL13 18.00 dBSFO2 400.1316005 MHz
F2 - Processing parametersSI 32768SF 100.6127353 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
O
OHO
3
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NMR spectra for trimethyl(6-(3-methylbut-2-enyl)benzo[d][1,3]dioxol-5-yloxy)silane, 6
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5 ppm
0.26
12
1.69
871.
7415
1.74
31
3.17
833.
1965
5.21
285.
2162
5.21
955.
2311
5.23
455.
2377
5.24
945.
2528
5.25
595.
8717
6.38
016.
6187
9.38
3.12
3.10
2.07
1.01
2.07
1.00
1.01
Current Data ParametersNAME WM-327EXPNO 3PROCNO 1
F2 - Acquisition ParametersDate_ 20100422Time 12.27INSTRUM dpx400PROBHD 5 mm QNP 1H/1PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 8278.146 HzFIDRES 0.126314 HzAQ 3.9584243 secRG 64DW 60.400 usecDE 6.00 usecTE 290.6 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 8.40 usecPL1 -3.00 dBSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300099 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
0.72
32
18.1
369
26.1
144
28.7
274
101.
2001
101.
6762
109.
2922
123.
2813
124.
6604
132.
7490
142.
0437
145.
8694
147.
2982
Current Data ParametersNAME WM-327EXPNO 4PROCNO 1
F2 - Acquisition ParametersDate_ 20100422Time 12.30INSTRUM dpx400PROBHD 5 mm QNP 1H/1PULPROG zgpg30TD 65536SOLVENT CDCl3NS 64DS 4SWH 23980.814 HzFIDRES 0.365918 HzAQ 1.3664756 secRG 6502DW 20.850 usecDE 6.00 usecTE 290.9 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 8
======== CHANNEL f1 ========NUC1 13CP1 9.70 usecPL1 -3.00 dBSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 84.00 usecPL2 -3.00 dBPL12 18.00 dBPL13 18.00 dBSFO2 400.1316005 MHz
F2 - Processing parametersSI 32768SF 100.6127690 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
O
OMe3SiO
6
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NMR spectra for 6-allyl-6-(3-methylbut-2-enyl)benzo[d][1,3]dioxol-5(6H)-one, 2
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
1.56
581.
6231
1.62
492.
1603
2.17
352.
1921
2.20
782.
2264
2.24
082.
2594
2.47
952.
4982
2.51
452.
5331
2.56
952.
5876
2.60
282.
6209
4.90
474.
9271
4.92
984.
9321
4.95
254.
9550
4.95
744.
9738
5.01
625.
0209
5.41
435.
5457
5.59
825.
7968
5.80
85
3.07
2.95
2.15
1.03
1.09
3.33
1.00
2.29
2.02
Current Data ParametersNAME WM-340EXPNO 5PROCNO 1
F2 - Acquisition ParametersDate_ 20100521Time 15.34INSTRUM dpx400PROBHD 5 mm QNP 1H/1PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 8278.146 HzFIDRES 0.126314 HzAQ 3.9584243 secRG 181DW 60.400 usecDE 6.00 usecTE 292.9 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 8.40 usecPL1 -3.00 dBSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300109 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
2030405060708090100110120130140150160170180190200 ppm
18.3
964
26.2
650
39.6
229
45.0
697
54.4
313
99.9
086
101.
6318
109.
1483
118.
4176
118.
7250
133.
4605
135.
2508
144.
2712
164.
4040
202.
7954
Current Data ParametersNAME WM-340EXPNO 4PROCNO 1
F2 - Acquisition ParametersDate_ 20100520Time 12.16INSTRUM dpx400PROBHD 5 mm QNP 1H/1PULPROG zgpg30TD 65536SOLVENT CDCl3NS 256DS 4SWH 23980.814 HzFIDRES 0.365918 HzAQ 1.3664756 secRG 6502DW 20.850 usecDE 6.00 usecTE 292.9 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 8
======== CHANNEL f1 ========NUC1 13CP1 9.70 usecPL1 -3.00 dBSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 84.00 usecPL2 -3.00 dBPL12 18.00 dBPL13 18.00 dBSFO2 400.1316005 MHz
F2 - Processing parametersSI 32768SF 100.6127690 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
O
OO
2
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S11
NMR spectra for 7a-allyl-6-(3-methylbut-2-enyl)benzo[d][1,3]dioxol-5(7aH)-one, 1
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
1.60
291.
7435
2.35
382.
3728
2.38
812.
4072
2.57
932.
5970
2.61
362.
6313
2.91
062.
9312
2.95
632.
9746
3.00
223.
0206
3.04
563.
0639
5.13
915.
1414
5.55
235.
5794
5.61
55
6.55
986.
5639
6.56
81
3.04
3.14
1.00
1.04
2.02
3.01
3.95
0.95
Current Data ParametersNAME WM-352EXPNO 4PROCNO 1
F2 - Acquisition ParametersDate_ 20100607Time 15.57INSTRUM dpx400PROBHD 5 mm QNP 1H/1PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 8278.146 HzFIDRES 0.126314 HzAQ 3.9584243 secRG 203.2DW 60.400 usecDE 6.00 usecTE 566.6 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 8.40 usecPL1 -3.00 dBSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300096 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
2030405060708090100110120130140150160170180190 ppm
18.0
491
26.1
178
27.8
608
40.9
057
81.4
497
98.2
861
98.9
046
120.
2613
121.
2453
130.
5382
133.
9274
135.
2393
140.
7057
173.
9416
187.
9356
Current Data ParametersNAME WM-352EXPNO 7PROCNO 1
F2 - Acquisition ParametersDate_ 20100608Time 9.16INSTRUM dpx400PROBHD 5 mm QNP 1H/1PULPROG zgpg30TD 65536SOLVENT CDCl3NS 256DS 4SWH 23980.814 HzFIDRES 0.365918 HzAQ 1.3664756 secRG 16384DW 20.850 usecDE 6.00 usecTE 293.1 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 8
======== CHANNEL f1 ========NUC1 13CP1 9.70 usecPL1 -3.00 dBSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 84.00 usecPL2 -3.00 dBPL12 18.00 dBPL13 18.00 dBSFO2 400.1316005 MHz
F2 - Processing parametersSI 32768SF 100.6127690 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
O
OO
1
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2011
S12
NMR spectra for 6-(3-methylbut-2-enyl)-7a-(2,2,2-trifluoroethoxy)benzo[d][1,3]dioxol-5(7aH)-one, 7
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5 ppm
1.61
001.
7597
2.95
662.
9749
3.00
123.
0194
3.05
453.
0725
3.09
883.
1170
3.78
553.
8062
3.85
743.
8782
5.12
33
5.62
755.
6342
5.66
93
6.51
546.
5199
6.52
44
3.09
3.09
2.14
2.12
1.09
1.89
1.09
1.00
Current Data ParametersNAME WM-352EXPNO 2PROCNO 1
F2 - Acquisition ParametersDate_ 20100604Time 17.43INSTRUM dpx400PROBHD 5 mm QNP 1H/1PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 8278.146 HzFIDRES 0.126314 HzAQ 3.9584243 secRG 143.7DW 60.400 usecDE 6.00 usecTE 293.0 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 8.40 usecPL1 -3.00 dBSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300102 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm
18.0
372
26.1
193
28.0
959
98.2
035
99.3
557
99.9
049
119.
1625
122.
1910
124.
9502
125.
6455
136.
2769
144.
6955
167.
1206
186.
7913
Current Data ParametersNAME WM-352EXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20110411Time 13.12INSTRUM dpx400PROBHD 5 mm QNP 1H/1PULPROG zgpg30TD 65536SOLVENT CDCl3NS 160DS 4SWH 23980.814 HzFIDRES 0.365918 HzAQ 1.3664756 secRG 16384DW 20.850 usecDE 6.00 usecTE 291.5 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 8
======== CHANNEL f1 ========NUC1 13CP1 9.70 usecPL1 -3.00 dBSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 84.00 usecPL2 -3.00 dBPL12 16.08 dBPL13 18.00 dBSFO2 400.1316005 MHz
F2 - Processing parametersSI 32768SF 100.6127357 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
O
OO
O
CF37
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2011
S13
NMR spectra for illioliganone C
6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm1.
0784
1.81
371.
8173
1.84
121.
8447
2.21
902.
2344
2.24
562.
2606
2.46
332.
4775
2.48
952.
5037
3.05
173.
0644
3.28
723.
3204
3.32
423.
3331
3.33
703.
3424
3.34
623.
3550
3.35
88
4.97
90
5.45
965.
5424
5.88
245.
8956
5.78
1.12
1.12
1.37
1.15
0.99
1.08
2.88
1.00
2.62
1.06
1.24
Current Data ParametersNAME ARM-1136_500EXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20110421Time 10.05INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT AcetoneNS 16DS 2SWH 10000.000 HzFIDRES 0.152588 HzAQ 3.2768500 secRG 287DW 50.000 usecDE 6.00 usecTE 296.5 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 9.70 usecPL1 0.10 dBSFO1 500.1330633 MHz
F2 - Processing parametersSI 32768SF 500.1300085 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
2030405060708090100110120130140150160170180190200 ppm
25.4
244
25.7
376
43.3
135
46.9
245
52.3
779
72.5
884
76.6
231
99.6
709
102.
3791
108.
3667
117.
9654
134.
2885
145.
1400
163.
7661
202.
0132
Current Data ParametersNAME ARM-1136_500EXPNO 2PROCNO 1
F2 - Acquisition ParametersDate_ 20110421Time 10.11INSTRUM av500PROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT AcetoneNS 2527DS 4SWH 30030.029 HzFIDRES 0.458222 HzAQ 1.0912244 secRG 11500DW 16.650 usecDE 6.00 usecTE 297.7 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 256
======== CHANNEL f1 ========NUC1 13CP1 9.00 usecPL1 0.00 dBSFO1 125.7703637 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 0.00 dBPL12 18.00 dBPL13 18.00 dBSFO2 500.1320005 MHz
F2 - Processing parametersSI 32768SF 125.7576838 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.00
O
OO
OHOH
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2011
S14
NMR spectra for 6-allyl-6-((3,3-dimethyloxiran-2-yl)methyl)benzo[d][1,3]dioxol-5(6H)-one, 12
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
1.17
841.
1969
1.52
981.
5481
1.56
461.
5829
2.21
982.
2385
2.25
292.
2716
2.32
252.
3320
2.35
732.
3669
2.40
222.
4118
2.42
052.
4301
2.53
012.
5482
2.56
322.
5814
4.99
144.
9936
5.52
915.
6681
5.82
315.
8359
6.16
1.04
1.04
1.04
1.00
1.01
2.04
2.04
0.95
2.02
Current Data ParametersNAME WM-350EXPNO 4PROCNO 1
F2 - Acquisition ParametersDate_ 20100602Time 10.43INSTRUM dpx400PROBHD 5 mm QNP 1H/1PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 8278.146 HzFIDRES 0.126314 HzAQ 3.9584243 secRG 143.7DW 60.400 usecDE 6.00 usecTE 291.9 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 8.40 usecPL1 -3.00 dBSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300000 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
2030405060708090100110120130140150160170180190200 ppm
19.2
185
25.0
004
40.3
508
46.3
770
53.2
989
58.1
443
61.2
795
99.7
573
101.
9560
108.
9594
119.
1387
132.
5347
144.
3427
165.
1492
202.
4055
Current Data ParametersNAME WM-350EXPNO 5PROCNO 1
F2 - Acquisition ParametersDate_ 20100602Time 10.28INSTRUM dpx400PROBHD 5 mm QNP 1H/1PULPROG zgpg30TD 65536SOLVENT CDCl3NS 256DS 4SWH 23980.814 HzFIDRES 0.365918 HzAQ 1.3664756 secRG 16384DW 20.850 usecDE 6.00 usecTE 291.9 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 8
======== CHANNEL f1 ========NUC1 13CP1 9.70 usecPL1 -3.00 dBSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 84.00 usecPL2 -3.00 dBPL12 18.00 dBPL13 18.00 dBSFO2 400.1316005 MHz
F2 - Processing parametersSI 32768SF 100.6127690 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
O
OO
O12
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2011
S15
NMR spectra for 6-allyl-6-(2,3-dihydroxy-3-methylbutyl)benzo[d][1,3]dioxol-5(6H)-one, 11
0.51.01.52.02.53.03.54.04.55.05.56.06.5 ppm1.
0318
1.04
851.
5172
1.54
071.
5520
1.57
542.
0670
2.17
212.
2069
2.28
652.
3050
2.31
952.
3379
2.46
922.
4872
2.50
212.
5202
3.41
723.
6228
3.63
53
4.91
654.
9363
4.93
924.
9418
4.95
584.
9984
5.00
395.
5174
5.67
805.
9147
5.93
97
6.01
1.06
8.16
1.15
1.18
1.15
22.1
0
0.73
0.75
2.02
1.94
1.00
1.99
Current Data ParametersNAME WM-410EXPNO 4PROCNO 1
F2 - Acquisition ParametersDate_ 20101014Time 9.24INSTRUM dpx400PROBHD 5 mm QNP 1H/1PULPROG zg30TD 65536SOLVENT AcetonNS 16DS 2SWH 8278.146 HzFIDRES 0.126314 HzAQ 3.9584243 secRG 143.7DW 60.400 usecDE 6.00 usecTE 290.9 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 8.40 usecPL1 -3.00 dBSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300000 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
2030405060708090100110120130140150160170180190200 ppm
23.5
635
24.8
003
42.8
960
46.1
348
53.0
225
71.9
963
75.6
351
98.3
775
101.
8864
110.
0737
117.
2213
133.
3360
142.
8229
164.
9156
201.
5635
Current Data ParametersNAME WM-410EXPNO 5PROCNO 1
F2 - Acquisition ParametersDate_ 20101014Time 9.27INSTRUM dpx400PROBHD 5 mm QNP 1H/1PULPROG zgpg30TD 65536SOLVENT AcetonNS 256DS 4SWH 23980.814 HzFIDRES 0.365918 HzAQ 1.3664756 secRG 11585.2DW 20.850 usecDE 6.00 usecTE 291.1 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 8
======== CHANNEL f1 ========NUC1 13CP1 9.70 usecPL1 -3.00 dBSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 84.00 usecPL2 -3.00 dBPL12 18.00 dBPL13 18.00 dBSFO2 400.1316005 MHz
F2 - Processing parametersSI 32768SF 100.6127690 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
O
OO
OHOH 11
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2011