Stereocontrolled Synthesis of Carbocyclic Compounds with a Quaternary Carbon … · 2012. 6. 1. ·...

S1

[Supporting Information]

Stereocontrolled Synthesis of Carbocyclic Compounds with a Quaternary Carbon Atom based on SN2´ Alkylation of γ ,δ-Epoxy-α ,β-unsaturated Ketones

Fumihiko Yoshimura,* Ayano Kowata, and Keiji Tanino*

Department of Chemistry, Faculty of Science, Hokkaido University Sapporo 060-0810, Japan

List of Contents Experimental procedures and compound characterization for 12, 13-anti, 14, 15, and 13-syn S2

NOE data for structural assignments of 16a, 17a-anti, and 17a-syn S5

Copies of the 1H and 13C NMR spectra S6

HPLC chromatograms for (+)-26, (–)-17a-anti, and (+)-17a-syn S72

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

S2

Experimental procedure and compound characterization for 12, 13-anti, 14, 15, and 13-syn (E)-2-(((2S*,3S*)-3-((Benzyloxy)methyl)oxiran-2-yl)methylene)cyclohexanone (12): To a freshly

prepared THF solution of lithium diisopropylamide, which was prepared from i-Pr2NH (614 µL, 4.38 mmol) and n-BuLi (2.69 M in hexane, 1.6 mL, 4.38 mmol) in THF (12 mL) was added a solution of

cyclohexanone (432 µL, 4.17 mmol) in THF (1 mL) slowly at –78 °C and the stirring was continued at

this temperature for 2 h. Then, a solution of ZnBr2 (freshly dried, 939 mg, 4.17 mmol) in THF (4 mL)

was added, and the mixture was stirred at –78 °C for 2 h. A solution of aldehyde 10 (842 mg, 4.38

mmol) in THF (2 mL) was added at –78 °C, and the mixture was stirred at this temperature for an

additional 1 h. After a saturated aqueous solution of NH4Cl was added, the mixture was filtered through

a pad of Celite by the aid of EtOAc. The organic layer was separated and the aqueous layer was

extracted with EtOAc. The combined organic layers were washed with water and brine, dried over

MgSO4, and concentrated under reduced pressure. The crude aldol product 11 was used for next step

without further purification.

To a solution of the crude aldol product 11 in CH2Cl2 (14 mL) were added Et3N (1.4 mL, 10.0 mmol)

and MsCl (389 µL, 5.00 mmol) at 0 °C. After the solution was stirred at room temperature for 40 min, DBU (1.5 mL, 10.0 mmol) wad added, and the mixture was stirred at room temperature for 45 min. The

reaction was quenched with saturated aqueous NaHCO3 solution. After the layers were separated, the

aqueous layer was extracted with EtOAc. The combined organic layers were washed with brine, dried

over MgSO4, and concentrated under reduced pressure. The residue was purified by flash column

chromatography (SiO2, hexane/EtOAc = 5:1) twice to give trans-epoxide 12 (556 mg, 2.04 mmol, 49%

for 2 steps): Yellow oil; IR (neat) ν 2939, 2863, 1729, 1690, 1622, 1497, 1454, 1301, 1232, 1141, 1100,

880, 740 cm–1; 1H NMR (500 MHz, CDCl3) δ 7.38–7.27 (m, 5H), 6.09 (dt, J = 9.2, 1.7 Hz, 1H), 4.59 (d, J = 12.1 Hz, 1H), 4.56 (d, J = 12.0 Hz, 1H), 3.77 (dd, J = 11.5, 2.9 Hz, 1H), 3.58 (dd, J = 11.5, 5.2 Hz,

1H), 3.51 (dd, J = 9.2, 3.2 Hz, 1H), 3.22 (quintet, J = 2.3 Hz, 1H), 2.77–2.65 (m, 1H), 2.58–2.39 (m,

3H), 1.94–1.74 (m, 4H); 13C NMR (125.8 MHz, CDCl3) δ 200.1, 141.3, 137.6, 133.2, 128.4, 127.8, 127.7, 73.4, 69.2, 58.6, 51.2, 40.2, 27.2, 23.4, 23.3; MS (FI) m/z 272 (M+, 100%); HRHS (FI) calcd for

C17H20O3 (M+): 272.1412, found: 272.1405.

SN2´ methylation reaction of 12: To a mixture of trans-epoxide 12 (38.0 mg, 0.140 mmol) and CuCN

(26.3 mg, 0.294 mmol) in DMF (350 µL) was added Me2Zn (2.0 M in toluene, 147 µL, 0.294 mmol) at –50 °C. After the reaction mixture was stirred at this temperature for 1 h, it was quenched by the

addition of a mixture of saturated aqueous NH4Cl and 35% aqueous NH4OH (9:1) and extracted with

Et2O. The combined organic layers were washed with water and brine, dried over MgSO4, and


S3

concentrated under reduced pressure to give 48.6 mg of the crude methylation products 13-anti and 14.

Yields of 13-anti and 14 were determined by 1H NMR using pyrazine as an internal standard. For

characterization, the mixture of the crude products was purified by preparative thin layer

chromatography (hexane/EtOAc = 1.2:1) to afford analytically pure samples.

(R*)-2-((3R*,1E)-4-(Benzyloxy)-3-hydroxybut-1-en-1-yl)-2-methylcyclohexanone (13-anti):

Colorless oil; IR (neat) ν 3446, 2931, 2861, 1706, 1452, 1117, 974, 907, 739, 699 cm–1; 1H NMR (500

MHz, CDCl3) δ 7.37–7.27 (m, 5H), 5.98 (dd, J = 16.1, 1.2 Hz, 1H), 5.40 (dd, J = 16.0, 5.7 Hz, 1H), 4.56 (s, 2H), 4.37–4.31 (m, 1H), 3.50 (dd, J = 9.8, 3.5 Hz, 1H), 3.34 (dd, J = 9.7, 8.1 Hz, 1H), 2.53 (d, J = 3.5

Hz, 1H), 2.48 (ddd, J = 14.4, 10.9, 5.8 Hz, 1H), 2.35–2.27 (m, 1H), 2.00–1.90 (m, 2H), 1.83–1.57 (m,

4H), 1.15 (s, 3H); 13C NMR (125.8 MHz, CDCl3) δ 213.2, 137.7, 136.7, 128.5, 128.4, 127.8, 127.7, 74.1, 73.3, 71.1, 51.1, 40.0, 39.2, 27.5, 24.0, 21.6; MS (FI) m/z 289 ([M+H]+, 100%); HRHS (FI) calcd for

C18H24O3 (M+): 288.1725, found: 288.1700.

(E)-2-(4-(Benzyloxy)-3-hydroxy-2-methylbutylidene)cyclohexanone (14): Colorless oil; IR (neat) ν

3444, 2932, 2867, 1684, 1614, 1143, 1100, 997, 817, 738, 699 cm–1; 1H NMR (500 MHz, CDCl3) δ 7.38–7.27 (m, 5H), 6.56 (brd, J = 9.8 Hz, 1H), 4.56 (d, J = 12.0 Hz, 1H), 4.53 (d, J = 12.0 Hz, 1H),

3.81–3.75 (m, 1H), 3.53 (dd, J = 9.2, 3.5 Hz, 1H), 3.40 (dd, J = 9.2, 7.4 Hz, 1H) 2.68–2.41 (m, 5H), 2.33

(d, J = 3.4 Hz, 1H), 1.88–1.68 (m, 4H), 1.01 (d, J = 6.9 Hz, 3H); 13C NMR (125.8 MHz, CDCl3) δ 201.2, 140.0, 137.8, 136.8, 128.4, 127.8, 127.7, 73.6, 73.4, 72.3, 40.2, 35.1, 26.9, 23.3, 23.3, 15.8; MS (FI) m/z

288 (M+, 100%); HRHS (FI) calcd for C18H24O3 (M+): 288.1725, found: 288.1730.

(E)-2-((2R*,3S*)-4-(Benzyloxy)-2-chloro-3-hydroxybutylidene)cyclohexanone (15): A mixture of

trans-epoxide 12 (150 mg, 0.550 mmol) and MgCl2 (262 mg, 2.75 mmol) in MeCN (2.8 mL) was stirred

at 50 °C for 12 h. After the mixture was cooled to room temperature, water was added, and the mixture

was extracted with EtOAc. The combined organic extracts were washed with water and brine, dried over

MgSO4, and concentrated under reduced pressure. The residue was quickly purified by flash column

chromatography (SiO2, hexane/EtOAc = 5:3) to afford chlorohydrin 15 (170 mg, 0.550 mmol, quant.):

Yellow oil; IR (neat) ν 3434, 2939, 2866, 1686, 1618, 1454, 1114, 916, 816, 738 cm–1; 1H NMR (500

MHz, CDCl3) δ 7.38–7.28 (m, 5H), 6.59 (dt, J = 10.3, 2.3 Hz, 1H), 4.72 (dd, J = 10.3, 6.3 Hz, 1H), 4.56

(s, 2H), 3.99 (quintet, J = 5.5 Hz, 1H), 3.69 (dd, J = 9.7, 5.7 Hz, 1H), 3.61 (dd, J = 9.7, 4.6 Hz, 1H), 2.71

(d, J = 5.2 Hz, 1H), 2.63 (dtd, J = 16.7, 5.7, 1.7 Hz, 1H), 2.53 (dtd, J = 16.1, 6.3, 1.7 Hz, 1H), 2.47 (t, J

= 6.3 Hz, 2H), 1.93–1.73 (m, 4H); 13C NMR (125.8 MHz, CDCl3) δ 200.6, 139.9, 137.5, 132.1, 128.5,

127.9, 127.8, 73.6, 73.2, 70.3, 55.8, 40.4, 27.2, 23.3, 23.2; MS (FD) m/z 308 (M+, 60%); HRHS (FD)


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calcd for C17H2135ClO3 (M+): 308.1179, found: 308,1183.

(S*)-2-((3R*,1E)-4-(Benzyloxy)-3-hydroxybut-1-en-1-yl)-2-methylcyclohexanone (13-syn): To a

mixture of chlorohydrin 15 (170 mg, 0.550 mmol) and CuCN (98.7 mmol, 1.10 mmol) in MeCN (3.7

mL) was added Me3Al (2.0 M in hexane, 1.1 mL, 2.20 mmol) at 0 °C. After the reaction mixture was

stirred at this temperature for 1 h, it was quenched by the addition of water, diluted with EtOAc, and

filtered through a pad of Celite, which was rinsed with EtOAc. The aqueous layer was extracted with

EtOAc, and the combined organic layers were washed with brine, dried over MgSO4, and concentrated

under reduced pressure. The residue was purified by flash column chromatography (SiO2,

hexane/EtOAc = 5:2) to afford methylation product 13-syn (123 mg, 0.425 mmol, 77% for 2 steps):

Colorless oil; IR (neat) ν 3443, 2929, 2861, 1707, 1497, 1453, 1117, 975, 907, 738, 699 cm–1; 1H NMR

(500 MHz, CDCl3) δ 7.32–7.27 (m, 5H), 5.96 (dd, J = 16.0, 1.2 Hz, 1H), 5.38 (dd, J = 16.1, 5.7 Hz, 1H),

4.55 (s, 2H), 4.36–4.31 (m, 1H), 3.50 (dd, J = 9.8, 3.5 Hz, 1H), 3.33 (dd, J = 9.2, 8.0 Hz, 1H), 2.55 (d, J

= 3.5 Hz, 1H), 2.50 (ddd, J = 14.3, 10.9, 5.2 Hz, 1H), 2.35–2.28 (m, 1H), 1.99–1.89 (m, 2H), 1.83–1.57

(m, 4H), 1.15 (s, 3H); 13C NMR (125.8 MHz, CDCl3) δ 213.3, 137.7, 136.9, 128.5, 128.4, 127.8, 127.7,

74.0, 73.3, 71.1, 51.1, 40.0, 39.2, 27.6, 24.3, 21.6; MS (FI) m/z 289 ([M+H]+, 100%); HRHS (FI) calcd

for C18H24O3 (M+): 288.1725, found: 288.1722.


S5

NOE data for structural assignments of 16a, 17a-anti, and 17a-syn

O

OBn

O

EtO16a

H H

NOE Figure S1. The key NOE for the determination of the configuration of 16a

Scheme S1. Determinations of the stereochemistries of 17a-anti and 17a-syn

O

OBn

Me OH

EtO17a-syn

1) H2, Pd/C

2) DIBALH then HCl (aq.)

OBn

Me OH

O

Triton-B O

Me

H

HOBn

O

OMe

HH

OBn

OH

O

OBn

Me OH

EtO17a-anti

1) H2, Pd/C

2) DIBALH then HCl (aq.)

O

Me

H

HOBn

O

RuCl3NaIO4 O

Me

H

HOBz

O

OMeH

HOBz

O

NOEs

NOEsH


S6

O

OBn12

O

PPM

108

64

20

7.36767.36087.35287.34027.32877.32537.31047.30707.30017.29327.26006.10226.09766.09426.08396.07936.07594.57914.57453.78783.78213.76493.75803.59653.58623.57363.56333.51873.51523.50153.49693.22553.22093.21523.21063.20492.79382.48232.46972.45822.44682.44222.42961.84901.83301.82151.80781.80201.78371.77451.76541.6932


S7

O

OBn12

O

PPM

200150

10050

0

200.0539

141.2692137.6256133.2475128.4116127.8011127.7153

77.2575 77.0000 76.7520 73.3754 69.1786 58.6006

51.2274

40.1535

27.2290 23.4328 23.2515


S8

O

OBn13-anti

MeOH

PPM

108

64

20

7.36887.35397.34477.34027.32647.31387.29667.26005.99235.99005.96025.95795.42205.41055.38995.37854.55623.51413.50723.49463.48773.35383.33773.33543.31832.53382.52692.32881.94751.94061.71961.71161.70351.69551.68871.61541.1527


S9

O

OBn13-anti

MeOH

PPM

200175

150125

10075

5025

213.1787

137.7305136.6527128.4783128.4497127.8202127.7248

77.2480 77.0000 76.7425 74.0527 73.3087 71.1149

51.0653

40.0104 39.1615

27.5438 24.0146 21.5919


S10

O

OBn13-syn

MeOH

PPM

108

64

20

7.36887.35517.34027.32647.31277.29787.26005.97855.97625.94655.94425.39915.38765.36705.35564.55393.51073.50383.49123.48433.34803.33203.32973.31372.55442.54752.48002.32772.32541.94061.93721.73681.70931.70351.69671.68181.61081.1458


S11

O

OBn13-syn

MeOH

PPM

200175

150125

10075

5025

213.2836

137.7210136.8625128.5356128.4497127.8297127.7343

77.2575 77.0000 76.7520 74.0240 73.2991 71.1244

51.1130

40.0199 39.1710

27.5629 24.2531 21.6491


S12

O

OBn14Me

OH

PPM

108

64

20

7.36997.35517.34137.32647.31387.29897.26006.56036.54084.54133.73173.71913.53933.53363.52103.51413.41673.40193.39843.38242.64032.63342.62662.61972.53722.48572.47082.44792.43532.42162.33452.32771.86501.85361.84671.84101.83411.75851.74711.73451.72191.68291.01411.0004


S13

O

OBn14Me

OH

PPM

200175

150125

10075

5025

201.1985

139.9720137.7782136.8053128.4116127.7725127.6962

77.2480 77.0000 76.7425 73.6425 73.4041 72.2976

40.2011

35.0505

26.8856 23.6331 23.2897 15.8212


S14

O

OBn15Cl

OH

PPM

108

64

20

7.37457.37117.36087.35737.35057.34597.32647.32187.31157.30707.29217.26006.60276.59926.59466.58326.57866.57404.73944.72684.71884.70624.55624.00083.99053.97903.70763.69623.68823.67673.62173.61263.60233.59312.71132.70102.62082.61632.54642.54182.52812.48002.46622.45361.88681.87531.86161.85011.78831.77571.76311.7516


S15

O

OBn15Cl

OH

PPM

200175

150125

10075

5025

200.6167

139.9339137.4825132.0743128.4783127.9156127.7630

77.2575 77.0000 76.7520 73.5757 73.2324 70.2755

55.7772

40.3824

27.1813 23.3469 23.1848


S16

PPM

108

64

20

7.35907.35107.34647.2616

6.22526.2069

5.48554.59114.58763.95323.93943.80433.79863.78143.77453.62113.61193.59823.58793.58333.56843.56503.24322.5045

1.39481.38111.3674

0.0000


S17

PPM

200150

10050

0

187.5778

176.9998

138.4745137.7114130.9678128.4497127.8202127.7534

102.8489

77.2480 77.0000 76.7425 73.4422 69.2263 64.5239 58.7818 51.5613

28.6979 24.1386

14.1043


S18

PPM

108

64

20

7.34757.33957.2639

6.37876.36275.48774.63574.61284.53274.50983.96923.95553.94063.92693.73453.72643.71963.71163.70353.61193.59823.58903.57643.45733.44472.50112.48392.1701

1.39711.38341.3696

0.0000


S19

PPM

200150

10050

0

187.1963

176.9712

139.1422137.6160128.3543128.2303127.8870127.7248

102.7249

77.2480 77.0000 76.7425 73.2991 68.4346 64.4476 57.2747 52.0001

28.4976 24.0528

14.0280


S20

PPM

108

64

20

7.2628

6.21726.2001

5.4843

3.95433.94063.36113.35773.34403.33942.98672.9832

2.5057

1.57231.39711.38221.36850.98370.97000.95510.8829

0.0000


S21

PPM

200150

10050

0

187.6636

176.8663

137.6351132.0171

102.7630

77.2575 77.0000 76.7425

64.4190 60.2507 54.2320

33.9249 28.6598 24.0146 19.1310 14.0375 13.8181


S22

PPM

108

64

20

7.20326.16346.14515.40533.89023.87653.86163.84783.81923.81233.79523.78833.73793.72993.71383.70583.50893.50543.49173.48713.07033.06683.06343.05992.83432.83212.70722.44152.43012.41751.31701.30321.28950.83030.82450.8188

0.00690.0000-0.0057


S23

PPM

200150

10050

0

187.5969

176.9330

138.0548

131.2921

102.8012

77.2480 77.0000 76.7425 64.4571 62.4159 60.2221

51.5327

28.6502 25.7983 24.0623 18.2916 14.0661

-5.3634 -5.3825


S24

PPM

108

64

20

7.35677.34417.3304

6.18636.1703

5.46944.58534.58084.10894.09523.77573.76883.60623.59593.43103.42753.41503.41043.31303.29593.22833.2237

1.44641.43261.4189


S25

PPM

200150

10050

0

192.7571

185.6320

137.6733137.5970128.4211127.8107127.7153126.7901

105.7008

77.2575 77.0000 76.7520 73.4041 69.1690 67.6715 58.6864 52.5342

32.1985

14.0757


S26

PPM

108

64

20

7.36137.35907.35677.34527.32927.31667.26285.90465.90235.87255.87025.48325.47175.45115.43965.29544.55563.89143.88333.87763.86963.51923.51233.49973.49283.34853.33253.33023.3130

2.3419

1.9422

1.36741.35251.33871.2013

0.0000


S27

PPM

200150

10050

0

201.3130

176.3512

137.8068135.1361128.4116127.7820127.7534127.7057

101.5898

77.2575 77.0000 76.7425 74.1480 73.2610 71.0862 64.1900

46.0386

33.6006

26.3229 23.4518

14.0948


S28

PPM

108

64

20

7.35557.35337.34187.32587.31207.29717.26395.87835.87605.84625.84395.45805.44545.42595.41335.29654.55103.88913.88103.87533.86733.49973.48713.48023.34623.33023.3279

2.47702.47132.3350

1.92391.67081.36391.34901.33531.2024

0.0000


S29

PPM

200150

10050

0

201.3225

176.4466

137.8259135.5558128.4402127.7916127.7534127.7343

101.6852

77.2575 77.0000 76.7520 74.1385 73.2991 71.2389 64.2186

46.1054

33.6102

26.3897 23.7761

14.1138


S30

PPM

108

64

20

7.2788

5.76035.75805.72825.72595.50035.48665.46835.45455.3045

3.90513.89823.89143.8833

2.3579

1.94341.37311.35931.34451.20700.92300.90810.8932

0.0000


S31

PPM

200150

10050

0

201.6564

176.3130

133.4573132.6466128.2399

101.5516

77.2575 77.0000 76.7425 72.4788 64.1805

45.8574

39.3236 33.4957 26.3420 23.5949 18.5301 14.0471 13.9040


S32

PPM

108

64

20

5.73745.70535.49925.3034

3.90393.89823.88913.8845

2.3614

1.93311.37191.35821.34451.20930.91840.90360.8898


S33

PPM

200150

10050

0

201.7327

176.3703

133.6672132.7038128.2685

101.5707

77.2575 77.0000 76.7520 72.5742 64.2091

45.9241

39.3141 33.6865 26.3706 23.4328 18.5491 14.0757 13.9326


S34

PPM

108

64

20

7.2147

5.81645.81415.78435.78215.40195.39045.36985.35835.2324

3.83183.82383.81813.80893.56503.54553.53753.36343.34853.3440

2.52512.51942.2766

1.8838

1.30441.28951.27571.14060.82910.8165

0.0000


S35

PPM

200150

10050

0

201.3130

176.3035

135.0312

127.9919

101.6184

77.2575 77.0000 76.7520 72.5170 67.0706 64.1614

46.0768

33.6769 26.3610 25.8174 23.5091 18.2344 14.1043

-5.3920 -5.4302


S36

PPM

108

64

20

7.2124

5.79925.76725.76495.36985.35725.33775.24153.83293.82613.81923.81233.55583.54783.53523.52833.35773.34173.33713.32222.27431.87121.30781.29411.28031.14860.83830.83260.00340.0000-0.0057-0.0172-0.0595


S37

PPM

200150

10050

0

201.3321

176.4275

135.4222

127.9537

101.6852

77.2480 77.0000 76.7425 72.5838 67.0134 64.1710

46.1149

33.6292 26.3897 25.8174 23.8811 18.2153 14.0948

-5.4111 -5.4493


S38

PPM

108

64

20

7.35677.34297.33497.2628

5.81075.8084

5.1866

4.5624

4.05744.0437

3.51803.51113.36462.72782.72552.50682.50452.4690

1.42811.41321.39941.2723

0.0000


S39

PPM

200150

10050

0

207.4175

187.3680

137.8068135.6893128.4497127.8107127.7725127.4005

101.8760

77.2575 77.0000 76.7520 74.0908 73.2991 71.1625 67.6620

49.4342

43.1008

23.3755

14.1234


S40

PPM

108

64

20

7.34987.34757.33617.3281

5.82905.82675.5553

5.1763

4.55674.5521

4.05054.0368

3.49863.3451

2.72552.72332.49772.4954

1.42351.40971.39481.2792


S41

PPM

200150

10050

0

207.5034

187.2440

137.8068135.5081128.4116127.7439127.7248127.2574

101.8187

77.2480 77.0000 76.7425 74.0336 73.2514 71.0099 67.6143

49.3484

42.9100

23.8620

14.0948


S42

PPM

108

64

20

7.35907.34527.33267.31897.30407.26396.69826.6776

5.50264.83044.81784.80984.79724.56364.01053.94523.93143.71733.70703.65543.64632.77822.76792.75652.49542.48282.4702

1.38911.37541.3616

0.0000


S43

PPM

200150

10050

0

187.9212

177.2287

137.5874137.1868130.1666128.4211127.8297127.7057

103.0682

77.2480 77.0000 76.7425 73.5567 73.2896 70.3899 64.5620 56.1683

31.5213 28.5930 24.2340 22.5934 14.0566


S44

PPM

108

64

20

7.34297.34077.32927.30977.30527.29607.28917.26516.68106.65935.50724.91864.90604.89684.88424.54304.52583.96463.95093.94633.93723.92343.65773.64973.63833.62913.55703.54783.53752.76792.75652.4370

2.0430

1.39371.38001.36621.2574

0.0000


S45

PPM

200150

10050

0

187.8449

177.2573

137.5397136.7099129.6229128.4306127.8393127.6867

103.1350

77.2575 77.0000 76.7425 73.6330 73.2896 70.3136 64.6002 58.8104

28.5358 24.1768

14.0757


S46

PPM

108

64

20

7.2719

6.70516.6845

5.5072

4.68044.67014.65864.6495

3.95553.9417

2.53322.52172.4931

1.57231.56321.39481.38111.36740.95170.93790.9230


S47

PPM

200150

10050

0

187.9212

177.1906

137.0533

129.9091

103.1350

77.2575 77.0000 76.7520 74.1194 64.6193 60.6990

34.9741 28.6693 24.3198 18.8830 14.0852 13.9040


S48

PPM

108

64

20

6.61586.5951

5.40534.68844.67584.66784.65523.86623.85243.83753.82383.75513.74133.63833.62802.76102.75072.65682.64422.64082.41522.4003

1.29181.27691.26310.80740.80160.79590.7810

0.0000-0.0069-0.0172


S49

PPM

200150

10050

0

187.8544

177.0475

136.9865

130.3765

103.0969

77.2480 77.0000 76.7425 74.3388 64.5143 63.2362 55.8154

28.5930 25.7697 24.2054 18.1676 14.0566

-5.4493 -5.4874


S50

PPM

108

64

20

7.35337.35107.33957.31897.30527.30177.26516.58146.5608

5.4797

4.54984.11244.10094.08723.69443.68413.63023.61993.24203.20082.85612.8458

2.0430

1.44181.42811.41321.2574

0.0000


S51

PPM

200150

10050

0

193.0433

185.5461

137.4634137.2154128.4688127.9156127.7916126.1510

106.1873

77.2480 77.0000 76.7425 73.5948 73.0988 70.2946 67.7192 57.9615

32.1317

14.0948


S52

PPM

108

64

20

7.36597.35907.35217.33727.32467.31097.2582

5.85085.84855.44315.2816

4.55213.87653.86963.86273.85583.49403.48713.36573.3497

1.70521.35591.34221.32841.25510.88290.81310.79820.7833

0.0000


S53

PPM

200150

10050

0

201.0745

176.2367

137.8450134.1727128.4497128.3543127.7916127.7248

102.0763

77.2575 77.0000 76.7520 74.2625 73.3182 71.3247 64.1805

49.4342

29.2893 28.7265 26.0844

14.1329 8.3622


S54

PPM

108

64

20

7.35217.33727.32357.30977.2651

5.8450

5.2816

4.54753.87533.86963.86163.85473.48713.48023.3359

2.4782

1.35701.34331.32840.83710.82220.8074

0.0000


S55

PPM

200150

10050

0

201.0554

176.2653

137.8354134.5638128.4211128.3257127.7630127.7057

102.0953

77.2575 77.0000 76.7520 74.2053 73.2801 71.3819 64.1614

49.4724

29.4324 28.8219 26.0844

14.1043 8.3813


S56

PPM

108

64

20

7.35447.34077.32817.31437.29717.2628

5.90005.8679

5.2793

4.55673.88103.87423.86733.86043.49513.48823.3508

1.62731.36621.36051.35481.34561.33191.28031.26541.25971.24480.88410.87490.86120.84630.0000


S57

PPM

200150

10050

0

201.1127

176.2177

137.8450134.5066128.4497128.3257128.1063127.7916127.7248

102.0286

77.2480 77.0000 76.7425 74.2434 73.3182 71.3056 64.1805

49.2530

36.4526 29.3561 26.1417 23.2229 14.1329 13.9898


S58

PPM

108

64

20

7.35217.33727.32357.30977.29377.2651

5.88975.8576

5.2759

4.54753.87533.86843.86163.85473.48603.47913.34973.3336

2.47482.4702

1.35701.34331.32841.26771.25510.88060.86690.8520

0.0000


S59

PPM

200150

10050

0

201.1031

176.2367

137.8259134.9262128.4306128.0587127.7630127.7057

102.0381

77.2480 77.0000 76.7425 74.1957 73.2801 71.3915 64.1519

49.2912

36.5957 29.4228 26.1321 23.2229 14.1043 13.9708


S60

PPM

108

64

20

7.35217.33727.32467.31097.29377.2628

5.87255.87025.84055.83825.48205.47065.28054.55333.86963.86043.85583.84673.49743.49053.37833.36233.3588

1.35251.33871.32380.82910.81540.80850.7948

0.0000


S61

PPM

200150

10050

0

200.9601

176.0555

137.8354133.4001128.9839128.4211127.7534127.6962

102.5341

77.2575 77.0000 76.7425 74.2720 73.2896 71.4296 64.1137 52.4102

32.3511 25.8364 24.2626 18.0532 16.7178 14.1138


S62

PPM

108

64

20

7.35557.34187.32817.31437.2616

5.87485.84285.84055.47065.2828

4.55673.87303.86393.85813.84903.50083.49513.37723.36113.35882.37512.32931.55971.35591.34101.32731.25400.83030.81650.80960.79590.06990.0000


S63

PPM

200150

10050

0

176.0555

137.8354133.7340128.9457128.4402127.7725127.7057

102.5436

77.2575 77.0000 76.7425 74.2243 73.2896 71.4964 64.1233 52.4484

32.5228 25.8555 24.5869 18.1199 16.7464 14.1234


S64

PPM

108

64

20

7.35337.33957.32697.31327.2616

5.92645.89315.33665.19115.16945.07435.03884.5556

3.88913.8753

2.41752.04422.03271.63421.36391.35021.3364

0.0000


S65

PPM

200150

10050

0

199.0142

176.7041

139.2185137.8164133.7149129.2986128.4306128.2971127.7820127.7343115.4585

101.8664

77.2480 77.0000 76.7425 74.0622 73.2991 71.2389 64.3236 52.9348

31.0157 26.2752

14.0852


S66

PPM

108

64

20

7.34187.32927.26287.2605

5.2106

4.47654.01164.00013.88453.8707

2.94892.8595

2.36712.3534

1.62271.36621.35251.33761.0467

0.0000-0.0034


S67

PPM

200150

10050

0

203.3923

176.0555171.5820

138.3123132.3318129.7755128.3162127.6867127.5245

101.1701

77.2480 77.0000 76.7425 71.6299 70.3422 64.2186

45.4377 41.5556 37.2347 35.4511 33.2572 31.9696 25.4930 18.2439 14.1138


S68

PPM

108

64

20

7.34877.34077.2616

5.6080

5.2667

4.49723.99213.98413.88913.8742

1.58381.37081.35591.34221.03750.96310.9494

0.0000


S69

PPM

200150

10050

0

175.6740

138.4077135.3269128.3448127.8107127.5722127.5340

101.9523

77.2575 77.0000 76.7520 71.8112 70.8287 64.1328

46.2771 40.7925

27.8109 25.7124 21.0196 15.5255 14.1520


S70

PPM

108

64

20

7.36137.35907.34757.32587.32237.31207.2628

5.90345.90125.73175.69965.69735.42595.4156

4.5601

3.53063.50543.34403.3279

2.53892.5320

1.89071.85291.8506

1.2528

0.8829

0.0000


S71

PPM

200150

10050

0

199.2527

165.3440

137.6733135.5367128.5070128.2208127.9919127.9060127.7630

77.2575 77.0000 76.7520 74.1385 73.3754 70.7715

41.3076 36.1855 34.0966

24.7586 20.7334


HOイへ ‘。0-

納~.告

-~. ()

情�

-$."

- 10).1)

2 4 5 4

- 12.. (1

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.喜

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- ~-1.1)

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3 4

-26.0

- :.穆 .0

刷� 30.a

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材� CAlぷ!LATIONRE汽lRT帥�

CH PKNO 11舵� AREA HEI鋭校� MK 1鋭� 110 α識調� C NA蝿E 1 3.637 9き� 12 告.D511

柵。 4.11苦� 105 21 9.85毛� 4.431 237 27 0.12総� 5.19晶� 24 事� 8.9127 事.815 22 き念� 9115

ー 301 5.争参事事皐事.3予告� 1118書�

1543 2. 智4624 li7lO.132ヲ� ID 1&.867 2O42 事事� v 1.9933 11 12.225 193宮l 313 き.5636 12 12.事毛� S 77203 2473 官� 41.3359 13 14.4苦器1192 2137 SV 43明.J717 14 16事58 12 1 9.0O晶2 15 17.392 岳き� TV 私事� 349 16 17.品25 H r官� 8.9253 17 17.858 57 TV 8.93事事�

TV :; 2 66争18.718 6.&354 一…一一一一一一一TOTAL 186778 5571 10母�

C-R8A CH阪測� ATOPACCH=1 R~port No. =7 [)ATA-I :tc階以I.C0b 19/82/27 12:45:12

S72


HO~払1

0.0

2‘日

3.6314.0 3‘� 839 4.4雪� 2

4.917 4.114

5. 167 5争� 42El 6.む� 6.97雪� 6.15El

事� .0 7.228

7.725 8.387

時� 1む.� (1

幽� 12.0

12.566

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C叩駐車� AC問機� ATOPACCH=1 Report No=10 DAT炉� 1:唾!CHRM1. CElS i告� IEl2l27 14:母音:金�

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TOTAL 100

S73


O ・� OH Me 11

雪̂/々、/ヘ

Jl J 6Bn EtO'¥"ま)-11a-anti

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綱� 2. (1

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情日 ig: ;:?嘉正義 iEigM75

76..463132 §.874 る.持� 8

鳴い � la・� 3358??7887.鴎� 8 8.98.5る98-648

10・(1I9.る4G9事� ..a188ヲ8 10.032

18?;:畑� 11. 192

12.01 12.200

13.283

.1 4.91 1415.5.21る事8

礼� 733 10腿i1. 6品l

13.812

7. un 7.342

8.032 8‘187 9188

3 10.958 11.042

1f>.む 16.79争・�

18. (1

18金� 882

働� 20.0

- 2~. 合 I 23.716

判� CALCULATION詫芭開設� T** C粍� PK掲� TIME AREA 1 ' 51

'1 R 15.21品�

<:'1

41231

52 16.79事� 26135空6

53 18.腿� 2 2494246

54 20.3己7 4813

55 22‘� 272 5498

5る� 23.716 13114 一一一一一一一一一一一一一一ー�

TOTAL 5185529 133518

C-R8A CHROMATOPAC C俳� 1 Report No. =2る�

HEIGHT。� MK ID陶� C側� C NA純芭翁ぬ品� t

1575 56305 74121

128 148 431

T T T

V 6.7宮51 50.4018 48.1001sv 9.9事28 9. 19る� 0.252ヲ�

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19/93/98 21:92DATA=I:eCHRMl.C21

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13.35G - 14.0 14.G17

幽� 3晶，Ij� 15.163

17.945 “� 18.0

- 20.0

2ふる� G6

嚇� 22.0

22.岳5G

- 2..¥.0 23.781

綱� 26.詰�

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C-R8A CHRO援ATOPACCHぉ� 1 Report No.=39 DATAペ:傘叩閥� 1.C22 lG/93/98 21:53:

S75

…側

M HU

HIDNO むα唱C NA磁作巴� H '

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ALCULATIONREPORT"む紳�

CH PK TIME A HEIGHT CONC地 NAME註&A 阪冷却 �

3 3 6る� 11，事 0.e115 O8884.26 3 43e7 5.352事予

る 5.005 77 13 0.0134

3 9.<H8Y1 る13.798事告車

89948442 14. 175 28 零�

V 46. 1033 269243 15.17 19143るる事�

V V 0. 1878 45 18.22 1984 39空� V 9.658446 19.256 3799 81

、 .e96る22.658 38-1 容8 G

V El.El85 147823. 125 事告� VEl51 23.343 5 19 。‘El086 V

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.7毒事� - 18. i)

柵� 22. 0) 21.727

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7 5.547 10 4 ふ� 9918

44 lふ?毒事� 2i08fl3 9478 46.9395

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2毒91 §‘2 82 v雪8‘22舎4

52 23.5事2 182 9 9.El316 一帯一一一甲山叩相即時四ーーーー-

TOTAL .577El3El 24事毛3 1語。�

C-R8A C緑HOMATOPACCH惣� 1 詫E'port.No.=3 [lATA=l:脅CHRMl.C03 19/e3/10 11:34

S76


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CH PKNO TI総� AREA H霊100 M五� ID総�

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C-R8A f恥?附出=1 Report No吟ひATA=1:唾CM-u-1!??:

S77

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41 22.683 24 3 2 0.008343 23.383 35

0.044644 24.124 187 毛� 0.241445 25.432 1013 19 0.0114

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Stereocontrolled Synthesis of Carbocyclic Compounds with a Quaternary Carbon … · 2012. 6. 1. ·...

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