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[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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
S69
PPM
200150
10050
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175.6740
138.4077135.3269128.3448127.8107127.5722127.5340
101.9523
77.2575 77.0000 76.7520 71.8112 70.8287 64.1328
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27.8109 25.7124 21.0196 15.5255 14.1520
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
S70
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108
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7.36137.35907.34757.32587.32237.31207.2628
5.90345.90125.73175.69965.69735.42595.4156
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2.53892.5320
1.89071.85291.8506
1.2528
0.8829
0.0000
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
S71
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200150
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199.2527
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77.2575 77.0000 76.7520 74.1385 73.3754 70.7715
41.3076 36.1855 34.0966
24.7586 20.7334
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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