an oxidative hosomi-sakurai strategy toward the synthesis

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

Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2011

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.


S3

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.


S4

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.


S5

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.


S6

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.


S7

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.


S8

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


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


O

OHO

3


S9

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





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


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




O

OMe3SiO

6


S10

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





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






O

OO

2


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


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



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






O

OO

1


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





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






O

OO

O

CF37


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


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


O

OO

OHOH


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





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






O

OO

O12


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


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



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


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




O

OO

OHOH 11


an oxidative hosomi-sakurai strategy toward the synthesis

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