Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
Novel Dienone-Phenol Type Rearrangement of
4,4-Disubstituted Cyclohexadienone System
Using Thiosilane
Yasufumi Wada†, Kouji Otani, Noriko Endo, Yasuyuki Kita and Hiromichi Fujioka*
Graduate School of Pharmaceutical Sciences, Osaka University, 1-6, Yamada-oka,
Suita, Osaka 565-0871, Japan.
E-mail: fujioka@phs.osaka-u.ac.jp; Fax: +81-6-6879-8229;
Tel: +81-6-6879-8225
Contents
1. General techniques-------------------------------------------------------------------S2
2. Synthesis of dienone compounds---------------------------------------------------S2
3. The reaction of dienone phenol type rearrangement-----------------------------S3
4. References-----------------------------------------------------------------------------S6
5. 1H NMR and 13C NMR spectra-----------------------------------------------------S7
1
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
General techniques
The 1H NMR and 13C NMR spectra were measured at JEOL JNM-LA500, JEOL
JNM-AL300 with tetramethylsilane as the internal standard at 20-25 oC. IR spectra were
recorded by a diffuse reflectance measurement of samples dispered in KBr powder. E.
Merck silica gel 60 was used for column chromatography.
1. Synthesis of dienone compounds
Synthesis of 1a-d was followed by ref 1.
Compound 1a,2) 1b,3) 1c and 1d1) are known compound.
Compound 6c is known compound.4)
Compound 6d:
O
O
O
MeO
O
TFA
THF
89%
N
H
O
5)
N, O-acetal
N
H
O
6d
Trifluoroacetic acid (TFA) (73 μl, 0.949 mmol) was added to a solution of N,O-acetal
(30.5 mg, 0.095 mmol) in tetrahydrofuran (THF) (6.0 mL) at 0 ℃ under N2. The
mixture was stirred at rt for 3 days. The reaction was quenched with aq. NaHCO3 and
extracted with AcOEt. The organic layer was washed with brine, dried over Na2SO4,
and evaporated in vacuo. The residue was purified by SiO2 column chromatography
using hexane-AcOEt (2/1) as the eluent to give 6d (24.4 mg, 89%). Red solid: IR (KBr):
3332, 1660, 1614, 1593, 1566 cm-1; 1H-NMR (CDCl3):  = 4.26 (1H, d, J = 7.5 Hz),
6.21 (2H, d, J = 9.5 Hz), 6.39 (1H, dd, J = 4.8, 7.5 Hz), 7.16 (2H, d, J = 9.5 Hz), 7.67
(1H, t, J = 7.5 Hz), 7.75 (1H, t, J = 7.5 Hz), 8.03 (1H, d, J = 7.5 Hz), 8.07 (1H, d, J =
7.5 Hz); 13C-NMR (CDCl3):  = 106.1, 107.2, 108.4, 124.4, 125.4, 126.2, 126.6, 130.7,
132.7, 133.0, 135.3, 139.1, 153.0, 165.2, 180.0, 182.1. HR-FABMS calcd for
C18H11NO3 (M+) 289.0739. Found. 289.0740.
2
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
2. The reaction of dienone phenol type rearrangement
Genaral Procedure of Dienone Phenol-type Rearrangement for compound 2a-c,
3-5a, b and 6a, 6c-d
Synthesis of 2a-c, 3-5a, b and 6a, 6c-d (Table 1-3)
SR
O
TMSSR (1.1 equiv) R1
acid (0.1 equiv)
R1
2
3
R R
1a-d
CH2Cl2 (0.1 M)
reflux
R3
R2
2a-c, 3-5a, b
and 7a, 7c-d
A solution of 1a-d (1.0 equiv.) in CH2Cl2 (0.1 or 0.02 M) was heated to reflux. After
being stirred for 15 min, TMSSR (1.1 equiv.) and acid (0.1 equiv.) were added to the
resulting solution. The mixture was stirred at the same temperature for 12 h-7 days. The
reaction was quenched with H2O and extracted with AcOEt. The organic layer was
washed with brine, dried over Na2SO4, and evaporated in vacuo. The residue was
purified by SiO2 column chromatography using hexane-AcOEt (50/1 for 2a-c, 3a-b,
4a-b, 5a-b; 5/1 for 7a; 15/1 for 7c; 2/1 for 7d) as the eluent to give 2a-c, 3-5a, b and 6a,
6c-d (2a 81%; 2b 86%; 2c 84%; 3a 42%; 3b 32%; 4a 74%; 4b 89%; 5a 62%; 5b 51%;
7a 40%; 7c 86%; 7d 72%; no starting materials was recovered in every reaction.)
Compound 2a: colorless liquid: IR (KBr): 3005, 2921, 1610, 1597, 1583, 1511 cm-1;
H-NMR (CDCl3): 2.20 (3H,s), 2.21 (3H, s), 3.78 (3H, s), 4.03 (2H, s), 6.83 (2H, d,
J = 8.5 Hz), 7.01 (1H, d, J = 8.0 Hz), 7.05 (1H, d, J = 8.0 Hz), 7.11 (1H, s), 7.19 (1H, d,
1
J = 8.5 Hz); 13C-NMR (CDCl3):  19.0, 19.4, 38.8, 54.9, 113.5, 127.6, 129.5, 129.6,
129.8, 131.4, 132.7, 134.8, 136.8, 158.4. HR-FABMS calcd for C16H18NaOS (M+Na+)
281.0976. Found. 281.0971.
Compound 2b is known compound.6)
Compound 2c is known compound.7)
2,4,5-trimethylphenol is known compound.8)
Compound 3a: colorless liquid: IR (KBr): 2361 cm-1; 1H-NMR (CDCl3): 2.19 (3H,
s), 2.23 (3H, s), 2.29 (3H, s), 2.43 (3H, s), 6.93 (1H, s), 6.97 (1H, s) ; 13C-NMR
(CDCl3):  = 22.9, 23.0, 29.1, 29.2, 126.2, 129.0, 129.5, 129.6, 130.1, 133.0.
HR-FABMS calcd for C10H15S (M+H+) 167.0894. Found. 167.0903.
3
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
Compound 3b: colorless liquid: IR (KBr): 2856, 2247, 1738, 1433 cm-1; 1H-NMR
(CDCl3): 2.11 (3H, s), 2.16 (3H, s), 2.22 (3H, s), 6.98-7.16 (7H, m); 13C-NMR
(CDCl3):  = 19.1, 19.4, 20.0, 125.4, 127.8, 128.9, 129.0, 132.1, 135.1, 135.9, 137.4,
137.7, 138.6. HR-FABMS calcd for C15H16S (M+) 228.0973. Found.228.0990.
Compound 4a: colorless liquid: IR (KBr): 2918, 2847, 1590, 1491, 1439 cm-1; 1H-NMR
(CDCl3): 1.57-1.71 (4H, m), 1.82 (2H, quintet, J = 5.5 Hz), 2.47 (3H, s), 2.73-2.76
(4H, m), 6.99 (1H, dd, J = 2.0, 8.5 Hz), 7.00-7.03 (2H, m); 13C-NMR (CDCl3):  = 16.3,
28.2, 28.3, 32.7, 36.1, 36.7, 109.0, 124.3, 127.8, 129.6, 140.7, 144.1. HR-FABMS calcd
for C12H16S (M+) 192.0973. Found. 192.0971.
Compound 4b: colorless liquid: IR (KBr): 2920, 2849, 1581, 1477, 1439 cm-1; 1H-NMR
(CDCl3): 1.62-1.63 (4H, m), 1.82 (2H, quintet, J = 5.5 Hz), 2.72-2.78 (4H, m), 7.05
(1H, d, J = 7.0 Hz), 7.10 (1H, dd, J = 2.0, 7.0 Hz), 7.16 (1H, d, J = 2.0 Hz), 7.25-7.30
(5H, m); 13C-NMR (CDCl3):  = 28.2 (2C), 32.6, 36.3, 36.5, 126.4, 129.0, 129.6, 129.8,
130.0, 132.6, 137.0, 137.1, 143.2, 144.7. HR-FABMS calcd for C17H18S (M+) 254.1129.
Found. 254.1119.
Compound 5a is known compound.9)
Compound 5b is known compound.10)
Compound 7a: white solid : mp 99-102 oC; []D26 -108 (c 0.570, CHCl3); IR (KBr):
2359, 2341, 1771 cm-1; 1H-NMR (CDCl3): 1.40 (3H, d, J = 7.0 Hz), 1.70-1.77 (1H,
m), 1.90-1.96 (1H, m), 2.24 (3H, s), 2.44 (3H, s), 2.44 (3H, s), 2.43-2.44 (1H, m),
2.51-2.59 (2H, m), 2.75 (1H, dt, J = 5.0, 17.5 Hz), 5.64 (1H, d, J = 6.0 Hz), 7.07 (1H,
s); 13C-NMR (CDCl3):  = 14.5, 16.1, 16.3, 19.7, 23.4, 24.1, 40.5, 41.9, 75.7, 128.1,
130.2, 130.5, 133.1, 134.1, 135.8, 179.5. HR-FABMS calcd for C16H21O2S (M+H+).
277.1262 Found. 277.1270.
Compound 7c: Red solid: mp 192-195 oC; IR (KBr): 3344, 1710, 1672, 1624, 1597,
1568, 1523 cm-1; 1H-NMR (CDCl3):  2.50 (3H, s), 3.01 (1H, d, J = 4.0 Hz), 3.02 (1H,
s), 3.80-3.84 (2H, m), 6.61 (1H, br s), 7.03 (1H, d, J = 8.0 Hz), 7.16 (1H, dd, J = 2.0,
8.0 Hz), 7.50 (1H, d, J = 2.0 Hz), 7.64 (1H, t, J = 7.5 Hz), 7.76 (1H, t, J = 7.5 Hz), 8.07
(1H, d, J = 7.5 Hz), 8.21 (1H, d, J = 7.5 Hz); 13C-NMR (CDCl3):  = 16.5, 34.6, 51.2,
125.9, 126.7, 126.9, 128.5, 130.1, 131.9, 132.0, 133.8, 134.9, 135.3, 138.4, 143.7, 182.0,
4
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
182.2. HR-FABMS calcd for C19H16NO2S+ (M+H+) 322.0902. Found. 322.0901.
Compound 7d: Red solid : mp 193-195 oC; IR (KBr): 3321, 2916, 2359, 2345, 1666,
1601, 1566, 1495, 1445 cm-1; 1H-NMR (CDCl3):  (3H, s), 3.17 (1H, dd, J =
8.5, 12.0 Hz), 3.24 (1H, d, J = 12.0 Hz), 4.93 (1H, d, J = 8.5 Hz), 5.37 (1H, br s), 6.67
(1H, br s), 6.81 (1H, dd, J = 3.0, 8.0 Hz), 7.07 (1H, d, J = 3.0 Hz), 7.09 (1H, d, J = 8.0
Hz), 7.67 (1H, dd, J = 1, 7.5 Hz), 8.07 (1H, dd, J = 1, 7.5 Hz), 8.10 (1H, d, J = 7.5 Hz),
8.19 (1H, d, J = 7.5 Hz); 13C-NMR (CDCl3):  = 11.9, 39.6, 66.9, 114.5, 115.7, 118.8,
126.2, 127.0, 130.1, 130.2, 130.3, 132.5, 133.5, 135.0, 137.9, 142.5, 154.2, 181.7, 182.7.
HR-FABMS calcd for C19H16NO3S (M+H+). 338.0851 Found. 338.0847.
Synthesis of 7b
O
O
TMSSR (3.3 equiv)
acid (0.1 equiv)
SMe
H
H
H
O
H
O
H
+
CH2Cl2 (0.1 M)
reflux
H
6b
H
7b
H
MeS
H
7b'
A solution of 6b (63.8 mg, 0.224 mmol) in CH2Cl2 (2.2 ml) was heated to reflux. After
being stirred for 15 min, TMSSR (29.6 l, 0.246 mmol) and TfOH (2.0 l, 0.022 mmol)
were added to the resulting solution. After being stirred for 10 min, additional TMSSR
(29.6 l, 0.246 mmol) was added to the resulting solution. After being stirred for 10 min,
additional TMSSR (29.6 l, 0.246 mmol) was added to the resulting solution again. The
mixture was stirred at the same temperature for 6 days. The reaction was quenched with
H2O and extracted with AcOEt. The organic layer was washed with brine, dried over
Na2SO4, and evaporated in vacuo. The residue was purified by SiO2 column
chromatography using hexane-AcOEt (10/1) as the eluent to give 7b (37,5 mg, 0.114
mmol, 51%) and 7b’ (15.4 mg, 0.047 mmol, 21%).
7b: white solid : mp 136-139 oC; []D26 +320 (c 0.390, CHCl3); IR (KBr): 2924, 2855,
2359, 2340, 1583, 1477, 1439 cm-1; 1H-NMR (CDCl3): =0.95 (3H, s), 1.20-1.29 (2H,
m), 1.58-1.70 (4H, m), 1.83 (1H, dt, J = 3.0, 13.5 Hz), 1.91 (1H, dt, J = 2.5, 12.0 Hz),
2.01-2.04 (1H, m), 2.11-2.18 (1H, m), 2.21 (3H, s), 2.41 (3H, s), 2.50 (2H, dd, J = 8.0,
19.5 Hz), 2.64-2.71 (2H, m), 2.90 (1H, dd, J = 3.0, 14.0 Hz), 6.98 (1H, d, J = 7.9 Hz),
7.05 (1H, d, J = 7.9 Hz); 13C-NMR (CDCl3):  = 14.7, 18.0, 19.5, 21.5, 24.4, 28.2, 29.4,
32.1, 35.8, 40.6, 47.3, 48.7, 50.5, 125.2, 127.6, 133.6, 135.7, 137.2, 139.3, 220.5.
HR-FABMS calcd for C20H26OS (M+). 314.1704 Found. 314.1685.
7b’: white solid : mp 84-90 oC; []D24 -21.2 (c 0.153, CHCl3); 1H-NMR (CDCl3):
=0.96 (3H, s), 1.24-1.35 (2H, m), 1.54 (1H, td, J = 3.7, 13.5 Hz), 1.63-1.69 (4H, m),
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Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
1.85 (2H, dd, J = 3.0, 13.4 Hz), 2.00-2.04 (1H, m), 2.14 (1H, dt, J = 8.6, 19.5 Hz), 2.32
(3H, s), 2.45 (3H, s), 2.47-2.52 (2H, m), 2.75 (1H, d, J = 16.5 Hz), 2.91 (1H, td, J = 4.9,
16.5 Hz), 6.86 (1H, s), 6.90 (1H, s); 13C-NMR (CDCl3):  = 14.6, 15.9, 21.6, 22.2, 24.7,
27.0, 32.1, 32.2, 35.8, 41.2, 46.7, 48.6, 50.6, 125.3, 127.5, 134.7, 135.4, 137.8, 138.9,
220.4.
3. References
1) Kane, V. V., Synthetic Commun. 1976, 6, 237-242.
2) Chai, K. B.; Sampson, P., J. Org. Chem. 1993, 58, 6807-6813.
3) Cook, K. L.; Waring, A. J., JCS Perkin Trans 1. 1973, 529-537.
4) Aubart, K. M.; Heathcock, C. H., J. Org. Chem., 1999, 64, 16.
5) Tohma, H.; Harayama, Y.; Hashizume, M.; Iwata, M.; Kiyono, Y.; Egi, M.; Kita, Y., J.
Am. Chem. Soc., 2003, 125, 11235.
6) Biehl, E. R.; Razzuk, A.; Jovanovic, M. V.; Khanapure, S. P., J. Org. Chem. 1986, 51,
5157-60.
7) Baliah, V.; Uma, M., Tetrahedron, 1963, 455-464.
8) Feeney, J.; Heinrich, A., Chem. Commun. (London), 1966, 295-297.
9) Mimura, T.; Nakai, T., Chemistry Letters, 1980, 1099-1102.
10) Takaki, K.; Okada, M.; Yamada, M.; Negoro, K., JCS, Chem. Commun. 1980, 24,
1183-4.
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Supplementary Material (ESI) for Chemical Communications
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4. 1H NMR and 13C NMRspectra
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Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
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8
9
7.1254
7.1083
7.0314
6.9875
6.9716
6.9472
6.9314
6.7422
6.7264
2.00
0.98
2.03
2.00
7
6
5
3.9550
2.11
4
3.7012
3.08
3
2
2.1368
2.1282
6.03
1H Line
1
0
PPM
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
2a
SBnOMe-p
K:\¶ƒf[ƒ^\2a\gousei,wy812mono.als
1H Line
Tue Dec 5 19:17:56 2006
1H
non
500.00 MHz
160.00 KHz
2167.63 Hz
16384
10000.00 Hz
32
1.6384 sec
1.0000 sec
5.50 usec
1H
24.5 c
CDCL3
0.00 ppm
0.12 Hz
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This journal is (c) The Royal Society of Chemistry 2009
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8
gosuei.ko.242
17
7.1521
6.8789
6.8386
2.01
7
6
5
4
3
2.3383
2.1986
2.1383
2.1029
2
1
0
PPM
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
3a
SMe
K:\¶ƒf[ƒ^\3a.als
gosuei.ko.242
Thu Aug 28 17:02:45 2008
1H
NON
300.40 MHz
130.00 KHz
1150.00 Hz
32768
6006.01 Hz
16
5.4559 sec
1.5440 sec
5.80 usec
1H
20.2 c
CDCL3
0.00 ppm
0.12 Hz
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This journal is (c) The Royal Society of Chemistry 2009
3.00
3.02
3.04
3.04
150
125
132.9664
130.0645
129.6206
129.4809
128.9712
126.2419
gousei.ko.253
100
75
50
29.2378
29.0816
23.0147
22.9408
25
PPM
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
18
3a
SMe
K:\¶ƒf[ƒ^\3a13c.als
gousei.ko.253
Fri Sep 05 08:55:26 2008
13C
BCM
75.45 MHz
124.00 KHz
1840.00 Hz
32768
20356.23 Hz
10159
1.6097 sec
1.3900 sec
4.50 usec
1H
20.9 c
CDCL3
77.00 ppm
0.12 Hz
24
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This journal is (c) The Royal Society of Chemistry 2009
8
19
7.1625
7.1399
7.1155
7.0588
7.0320
7.0271
7.0039
6.9783
7.00
7
6
5
4
3
2.2212
2.1627
2.1133
2
1
0.0000
0
PPM
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
3.34
3.19
3.00
3b
SPh
Thu Aug 28 10:41:19 2008
1H
NON
300.40 MHz
130.00 KHz
1150.00 Hz
32768
6006.01 Hz
4
5.4559 sec
1.5440 sec
5.80 usec
1H
21.3 c
CDCL3
0.00 ppm
0.12 Hz
15
K:\¶ƒf[ƒ^\3b.als
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22
8
1H Line
23
7.2615
7.0319
7.0200
7.0026
6.9990
3.00
7
6
5
4
2.7645
2.7562
2.7498
2.7425
2.7343
2.4672
3
1.8323
1.8222
1.6347
2.05
2
1
0.0000
0
PPM
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
4a
SMe
K:\¶ƒf[ƒ^\4a\gousei.ko.92.nmdata
1H Line
Tue Nov 27 00:07:08 2007
1H
non
500.00 MHz
160.00 KHz
2167.63 Hz
32768
14992.50 Hz
16
1.6384 sec
1.0000 sec
5.50 usec
1H
16.4 c
CDCL3
0.00 ppm
0.12 Hz
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4.03
3.01
4.03
150
144.1273
140.7170
1H Line
129.5680
127.7462
124.3214
125
100
75
50
36.6741
36.1349
32.6517
28.3378
28.1921
25
24
0
PPM
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
4a
SMe
K:\¶ƒf[ƒ^\4a.13c\gousei.ko.92r.13c.nmdata
1H Line
Tue Nov 27 17:10:32 2007
13C
bcm
125.65 MHz
120.00 KHz
7958.00 Hz
16384
30030.03 Hz
3918
0.5456 sec
1.0000 sec
8.00 usec
1H
18.4 c
CDCL3
77.00 ppm
0.12 Hz
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16.2707
109.0334
109.0042
8.11
7
6
5
4
3
2
4.10
4.00
7.2072
7.2011
7.1950
7.1852
7.1791
7.1474
7.1339
7.1291
7.1230
7.1169
7.1120
7.0839
7.0436
7.0412
7.0290
7.0253
6.9851
6.9692
8
2.7115
2.6969
2.6896
2.6761
2.6676
2.6627
2.6554
1.7658
1.7548
1.7438
1.7316
1.5620
1.5522
1.5413
2.07
1H Line
1
0.0000
25
0
PPM
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
4b
SPh
J:\NMR\gousei.ko.51r\gousei.ko.51r.nmdata
1H Line
Sat Oct 13 14:10:26 2007
1H
non
500.00 MHz
160.00 KHz
2167.63 Hz
16384
10000.00 Hz
16
1.6384 sec
1.0000 sec
5.50 usec
1H
21.3 c
CDCL3
0.00 ppm
1.20 Hz
20
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
26
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
27
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
28
8
040297
29
7.1906
6.9405
6.9100
3.10
7
6
5
4
3
1.7309
1.7199
1.7095
1.6985
1.6876
2
1
0.0000
0
PPM
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
5a
SMe
J:\NMR\362.als
040297
Fri Feb 13 01:53:10 2009
1H
NON
300.40 MHz
130.00 KHz
1150.00 Hz
32768
6006.01 Hz
32
5.4559 sec
1.5440 sec
5.80 usec
1H
19.9 c
CDCL3
0.00 ppm
1.22 Hz
22
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
4.10
2.6719
4.05
3.4648
3.00
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
30
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
31
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
32
33
8
7.2645
7.0729
1.00
7
6
1.00
5
4
3
1.03
2.01
7.04
3.01
2
1.01
1.03
3.01
1
0
PPM
5.6452
5.6330
2.7799
2.7689
2.7579
2.7457
2.7347
2.7225
2.5871
2.5773
2.5700
2.5602
2.5480
2.5334
2.5248
2.5151
2.4382
2.4357
2.2429
1.9610
1.9501
1.9403
1.9232
1.9122
1.9025
1.7743
1.7634
1.7560
1.7463
1.7377
1.7280
1.7182
1.7097
1.6999
1.4058
1.3924
0.0024
0.0000
MeS
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
7a
Mon Aug 04 21:30:16 2008
1H
non
500.00 MHz
0.00 KHz
162160.00 Hz
16384
10000.00 Hz
22
1.6384 sec
1.0000 sec
5.40 usec
1H
21.7 c
CDCL3
0.00 ppm
0.12 Hz
22
K:\¶ƒf[ƒ^\7a.als
O
O
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
200
175
150
135.7647
134.0548
133.1012
130.4541
130.1910
128.0866
125
100
75.7208
75
50
24.0537
23.3879
19.7132
16.2770
16.0550
14.5013
25
34
0
PPM
MeS
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
7a
Sat Sep 13 08:54:02 2008
13C
BCM
75.45 MHz
124.00 KHz
1840.00 Hz
32768
20356.23 Hz
6638
1.6097 sec
1.0000 sec
4.50 usec
1H
20.9 c
CDCL3
0.00 ppm
0.12 Hz
24
K:\¶ƒf[ƒ^\7a 13c.als
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
O
O
41.8762
40.5280
179.4823
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
35
36
8
7.0607
7.0449
6.9887
6.9729
2.9141
2.9080
2.8860
2.8799
2.6896
2.6835
2.6652
2.6408
2.5492
2.5260
2.5102
2.4870
2.4711
2.4126
2.2100
2.1600
2.1221
2.0452
2.0428
2.0294
1.9318
1.9269
1.9220
1.9073
1.8476
1.8268
1.8207
1.8146
1.7011
1.6938
1.6840
1.6755
1.6560
1.6425
1.6340
1.6157
1.6084
1.2728
1.2630
1.2594
1.2569
1.2447
1.2398
1.2301
1.2069
0.9457
7
1.00
1.01
6
5
4
3
1.02
2.05
2.02
3.02
3.05
2
1.05
1.08
1.01
1.01
4.03
2.08
1
3.02
0
PPM
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
SMe
H
Tue Sep 09 14:00:39 2008
1H
non
500.00 MHz
0.00 KHz
162160.00 Hz
16384
10000.00 Hz
16
1.6384 sec
5.3616 sec
5.40 usec
1H
22.2 c
CDCL3
0.00 ppm
0.12 Hz
13
7b
H
H
O
J:\¶ƒf[ƒ^\7b .als
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
200
139.3418
137.1949
135.6567
133.5838
127.5874
125.1773
150
100
0
50.5300
48.7369
47.2892
40.5935
35.8062
32.0636
29.3903
28.2469
24.3809
21.4690
19.4784
17.9978
14.6747
50
PPM
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
SMe
H
37
7b
H
H
O
Tue Sep 09 13:53:23 2008
13C
bcm
125.65 MHz
0.00 KHz
127958.00 Hz
32768
33898.30 Hz
2621
0.9667 sec
1.5000 sec
5.00 usec
1H
22.8 c
CDCL3
77.00 ppm
0.12 Hz
26
J:\¶ƒf[ƒ^\7b.13c.als
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
220.4543
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
38
39
8
7.2600
6.9012
6.8585
2.9071
2.8986
2.7656
2.7326
2.5276
2.5118
2.5069
2.4996
2.4886
2.4727
2.4642
2.4507
2.3251
2.1725
2.1554
2.1383
2.1164
2.1005
2.0456
2.0358
2.0212
2.0053
1.8650
1.8589
1.8528
1.8382
1.8320
1.6942
1.6771
1.6636
1.6307
1.5746
1.5672
1.5477
1.5404
1.5221
1.5148
1.3195
1.3122
1.2963
1.2902
1.2744
1.2609
1.2561
1.2414
0.9559
0.0004
7
2.00
6
5
4
3
0.98
0.99
3.02
5.09
2
1.00
1.02
2.00
4.02
1.01
2.05
1
3.02
0
PPM
MeS
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
H
Thu Oct 30 17:27:06 2008
1H
non
500.00 MHz
0.00 KHz
162160.00 Hz
16384
10000.00 Hz
20
1.6384 sec
1.0000 sec
5.40 usec
1H
23.4 c
CDCL3
7.26 ppm
0.12 Hz
13
7b'
H
H
O
F:\7b'\HNMR@.als
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
200
138.9058
137.7789
135.4346
134.6779
127.5463
125.3336
150
100
50.5629
48.6217
46.6558
41.1529
35.7569
32.1541
32.1212
27.0213
24.7017
22.1929
21.5513
15.9085
14.5924
50
40
0
PPM
MeS
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
H
7b'
H
H
O
Thu Oct 30 19:08:55 2008
13C
bcm
125.65 MHz
0.00 KHz
127958.00 Hz
32768
33898.30 Hz
1200
0.9667 sec
2.0333 sec
5.00 usec
1H
25.4 c
CDCL3
77.00 ppm
0.12 Hz
24
F:\7b'\Cnmr.als
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
220.4296
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
41
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
42
8
7
2.04
2.10
2.00
6
8.2212
8.2054
8.0809
8.0650
7.7746
7.7600
7.7441
7.6538
7.6392
7.6245
7.5000
7.1730
7.1693
7.1571
7.1535
7.0400
7.0241
6.6092
1.06
0.80
5
3.8208
4
2.04
3.0239
3.0154
3.0069
3
2.00
1H Line
2
1
43
7c
NH
SMe
K:\¶ƒf[ƒ^\7c\gousei,wy854.nmdata
1H Line
Tue Jan 16 00:47:11 2007
1H
non
500.00 MHz
160.00 KHz
2167.63 Hz
16384
10000.00 Hz
32
1.6384 sec
3.0000 sec
5.50 usec
1H
22.9 c
CDCL3
0.00 ppm
0.12 Hz
25
O
0
PPM
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
O
3.06 2.5041
182.2088
181.9465
1H Line
175
125
143.6755
138.3560
135.3246
134.8874
133.8527
132.0455
131.9144
130.0635
128.4895
126.9155
126.6386
125.9245
150
100
75
51.2188
50
25
44
7c
NH
SMe
K:\¶ƒf[ƒ^\7c.13c\gousei,wy854Cnmr.nmdata
1H Line
Tue Jan 16 01:23:24 2007
13C
bcm
125.65 MHz
120.00 KHz
7958.00 Hz
16384
30030.03 Hz
701
0.5456 sec
2.4544 sec
8.00 usec
1H
23.6 c
CDCL3
77.00 ppm
0.12 Hz
30
O
0
PPM
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
O
16.4893
34.6483
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
45
8
1H Line
46
6
5
3
2
1
0
H
H
N
H
7c
SMe
K:\¶ƒf[ƒ^\7c.nOe\gousei,wy854nOe.nmdata
1H Line
Fri Jan 19 03:21:12 2007
1H
noe_dif
500.00 MHz
160.00 KHz
2167.63 Hz
16384
10000.00 Hz
64
1.6384 sec
5.3616 sec
11.20 usec
1H
23.3 c
CDCL3
7.06 ppm
0.12 Hz
17
O
3.8437
4.69
4
3.0407
3.0322
3.0236
3.0151
-100.00
8.08
7.0580
7.0421
7
PPM
n Oe
H
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
O
6
5
4
3
2
1
0.0000
K:\¶ƒf[ƒ^\6d\gousei,wy846up.nmdata
1H Line
Sat Jan 6 20:31:27 2007
1H
non
500.00 MHz
160.00 KHz
2167.63 Hz
16384
10000.00 Hz
32
1.6384 sec
5.3616 sec
5.60 usec
1H
17.2 c
CDCL3
0.00 ppm
0.12 Hz
27
47
N
H
O
6d
O
0
PPM
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
O
2.00
8
7
8.0797
8.0773
8.0650
8.0626
8.0333
8.0309
8.0187
8.0162
7.7710
7.7685
7.7563
7.7526
7.7404
7.7380
7.6880
7.6855
7.6733
7.6709
7.6587
7.6550
7.1730
7.1523
6.4005
6.3920
6.3859
6.3761
6.2175
6.1967
4.2674
4.2650
4.2528
4.2491
1H Line
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
1.03
1.01
2.01
2.09
2.16
175
182.0630
179.9498
1H Line
125
152.9590
139.1284
135.3246
132.9782
132.6868
130.7193
126.5512
126.1868
125.4144
124.4088
150
108.4358
107.1679
106.1040
100
75
50
25
K:\¶ƒf[ƒ^\6dCnmr\gousei,wy846upCnmr.nmdata
1H Line
Sun Jan 7 04:11:32 2007
13C
bcm
125.65 MHz
120.00 KHz
7958.00 Hz
16384
30030.03 Hz
5787
0.5456 sec
2.4544 sec
8.00 usec
1H
25.6 c
CDCL3
77.00 ppm
0.12 Hz
30
O
48
N
H
O
6d
O
0
PPM
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
169.7773
165.1719
49
8.2017
8.1859
8.1126
8.0968
7.7856
7.7832
7.7697
7.7673
7.7551
7.7526
7.6880
7.6855
7.6733
7.6709
7.6587
7.6550
7.2633
7.1022
7.0864
7.0693
7.0632
6.8228
6.8179
6.8069
6.8008
6.6739
5.3682
4.9508
4.9459
4.9410
4.9337
4.9288
4.9240
3.2485
3.2253
3.1899
3.1728
3.1618
3.1447
2.1746
2.00
8
2.01
2.00
7
1.03
1.00
6
1.02
5
1.01
4
2.40
3
3.57
2
1
0
PPM
0.0000
MeS
DFILE
COMNT
DATIM
OBNUC
EXMOD
OBFRQ
OBSET
OBFIN
POINT
FREQU
SCANS
ACQTM
PD
PW1
IRNUC
CTEMP
SLVNT
EXREF
BF
RGAIN
HO
7d
NH
Wed Jul 23 19:19:01 2008
1H
non
500.00 MHz
0.00 KHz
162160.00 Hz
16384
10000.00 Hz
125
1.6384 sec
1.0000 sec
5.40 usec
1H
21.1 c
CDCL3
0.00 ppm
0.12 Hz
23
K:\¶ƒf[ƒ^\7d.als
O
O
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
50
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
51
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
52