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Supporting Information
Dearomatisation approaches to Spirocyclic Dienones via the Electrophilic Activation of
Alkynes
Aimee K. Clarke, John T. R. Liddon, James D. Cuthbertson, Richard J. K. Taylor and
William P. Unsworth
Department of Chemistry, University of York, Heslington, York, YO10 3DD, U.K.
Table of Contents Page
Full optimisation table for spirocyclic dienone formation (Table S1) 2
HPLC data 3
1H and
13C NMR spectra 4–51
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2016
Table S1. Full optimisation of acid-catalysed ynone spirocyclisation
En
try
Yn
on
e
Catalyst Equiv/
Time [h]/ Temp [°C]
Conversion[a],[b]
(isolated yield in brackets)
1 9a SnCl2.2H2O 5/20/RT No Reaction
2 9a SnCl2.2H2O 5/20/45 No Reaction
3 9b SnCl2.2H2O 5/20/RT No Reaction
4 9b SnCl2.2H2O 5/20/45 No Reaction
5 9c SnCl2.2H2O 5/20/RT No Reaction
6 9c SnCl2.2H2O 5/20/45 10%
7 9d SnCl2.2H2O 5/20/RT 75% (57%)
8 9d SnCl2.2H2O H2O (50
eq.)
5/20/RT No Reaction
9 9d Dry SnCl2 5/20/RT 10%
10 9d SnCl2.2H2O 1/20/RT 65%
11 9d SnCl2.2H2O 0.1/72/RT 30%
12 9d Yb(OTf)2 1/20/RT No Reaction
13 9d Au(PPh3)Cl 1/20/RT No Reaction
14 9d Formic acid 1/20/RT No Reaction
15 9d Zn(OTf)2 1/20/RT No Reaction
16 9d ZnCl2 1/20/RT No Reaction
17 9d PdCl2(PPh3)2 1/20/RT No Reaction
18 9d Sc(OTf)3 1/20/RT 25%
9 9d SnCl4 1/20/RT 1:1 9d:10d mixture (with
impurities)
20 9d TFA 1/20/RT 3:1 9d:10d mixture (with
impurities)
21 9d BF3.OEt2 1/20/RT 1:9 9d:10d mixture (with
impurities)
22 9d c. HCl aq. 1/4/RT Complex mixture
23 9d TfOH 1/1/RT Complex mixture
24 9d p-TSA.H2O 1/20/RT Complex mixture
25 9d Au(PPh3)Cl and AgOTf 1/1/RT Complex mixture
26 9d AgOTf 1/20/RT 10%
27 9d AuCl3.H2O 1/0.25/RT Complex mixture
28 9d Cu(OTf)2 1/1/RT >95% (80%)
[a] All reactions performed on 0.09–0.2 mmol of ynone in CH2Cl2 (0.1M); [b] Conversion measured
from crude 1H NMR spectra.
CSP-HPLC of 12t using Chiralpak ID column, eluting with 20% IPA in hexanes.
1. Racemic 12t recorded at 280 nm
Peak
No.
Retention
Time / min
Peak
Area
Peak
Area / %
1 77.3 2726 50.2
2 87.5 2696 49.7
2. (+)12t recorded at 280 nm
Peak
No.
Retention
Time / min
Peak
Area
Peak
Area / %
1 72.8 47799 38.4
2 82.6 76541 61.6
j2793jdo_PROTON-1.jdf
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
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
2.003.632.001.012.152.142.06
j2795jdo_CARBON-1.jdf
200 180 160 140 120 100 80 60 40 20
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
j2859wpu_PROTON-1.jdf
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
Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
Norm
alized Inte
nsity
2.006.055.142.002.00
j2860wpu_CARBON-1.jdf
200 180 160 140 120 100 80 60 40 20
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
j4382jdc_PROTON-1.jdf
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
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
5.172.001.001.960.980.94
j4381jdc_CARBON-1.jdf
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
j5192wpu_PROTON-1.jdf
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
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
2.012.932.001.011.800.95
j5191wpu_CARBON-1.jdf
200 180 160 140 120 100 80 60 40 20
Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
Norm
alized Inte
nsity
j5152jdc_PROTON-1.jdf
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 0.5
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
3.001.001.033.253.243.330.932.142.22
j5151jdc_CARBON-1.jdf
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
j4683wpu_PROTON-1.jdf
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 0.5
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
2.870.860.911.006.083.942.301.83
j4684wpu_CARBON-1.jdf
180 160 140 120 100 80 60 40 20
Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
Norm
alized Inte
nsity
j4784wpu_PROTON-1.jdf
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 0.5
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
2.601.020.920.913.252.943.191.162.06
j4785wpu_CARBON-1.jdf
200 180 160 140 120 100 80 60 40 20
Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
Norm
alized Inte
nsity
j4309jdc_PROTON-1.jdf
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
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
2.9411.322.000.97
j4308jdc_CARBON-1.jdf
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20
Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
Norm
alized Inte
nsity
j4886jdc_PROTON-1.jdf
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
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
11.001.961.880.941.83
j4885jdc_CARBON-1.jdf
180 160 140 120 100 80 60 40 20
Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
Norm
alized Inte
nsity
j4781wpu_PROTON-1.jdf
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
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
0.960.973.032.981.000.961.971.961.94
j4782wpu_CARBON-1.jdf
200 180 160 140 120 100 80 60 40
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
j4958wpu_PROTON-1.jdf
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 0.5
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
11.242.001.932.110.97
j4959wpu_CARBON-1.jdf
180 160 140 120 100 80 60 40 20
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
j4984jdc_PROTON-1.jdf
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
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
2.006.434.152.961.18
j4983jdc_CARBON-1.jdf
200 180 160 140 120 100 80 60 40 20
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Norm
alized Inte
nsity
j5735jdc_PROTON-1.jdf
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 0.5 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
5.001.906.75
j5734jdc_CARBON-1.jdf
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30
Chemical Shift (ppm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
j5394jdc_PROTON-1.jdf
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
2.040.992.002.045.05
j5393jdc_CARBON-1.jdf
200 180 160 140 120 100 80 60 40
Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
Norm
alized Inte
nsity
j5038wpu_PROTON-1.jdf
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 0.5
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
3.976.144.001.911.89
j5039wpu_CARBON-1.jdf
200 180 160 140 120 100 80 60 40 20
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
j5050jdc_PROTON-1.jdf
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
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
1.931.993.151.012.012.061.992.00
j5048jdc_CARBON-1.jdf
200 180 160 140 120 100 80 60 40 20
Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
Norm
alized Inte
nsity
j6528wpu_PROTON-1.jdf
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 0.5
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
6.012.002.142.434.161.020.95
j6718wpu_CARBON-1.jdf
180 160 140 120 100 80 60 40 20
Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
Norm
alized Inte
nsity
j5655wpu_PROTON-1.jdf
9.0 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 0.5
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
3.001.914.813.051.910.87
j5656wpu_CARBON-1.jdf
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30
Chemical Shift (ppm)
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
Norm
alized Inte
nsity
P2758AKC_PROTON-1-1.JDF
10 9 8 7 6 5 4 3 2 1
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
3.005.062.112.11
P2758AKC_CARBON-1-1.JDF
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
P2561AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
2.000.921.951.951.963.00
P2561AKC_CARBON-1-1.JDF
180 160 140 120 100 80 60 40 20
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
N7474AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
2.002.051.112.232.301.182.14
N7525AKC_CARBON-1-1.JDF
200 180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
P8766AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
5.001.024.001.941.94
P8780AKC_CARBON-1-1.JDF
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
P6965AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
3.002.982.083.081.170.992.05
P6973AKC_CARBON-1-1.JDF
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
R0328AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
4.822.960.890.983.871.99
R0328AKC_CARBON-1-1.JDF
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
R0751AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
2.002.973.020.990.980.971.991.032.00
R0751AKC_CARBON-1-1.JDF
200 180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
R4235AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
3.032.082.062.032.000.932.001.98
R4235AKC_CARBON-1-1.JDF
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
P9943AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
3.672.892.311.991.950.961.942.00
P9974AKC_CARBON-1-1.JDF
200 180 160 140 120 100 80 60 40 20
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
R4428AKC_PROTON-1-1.JDF
8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
9.001.992.791.911.952.651.97
R4566AKC_CARBON-1-1.JDF
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
R4567AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
10.292.112.133.282.181.002.082.11
R4567AKC_CARBON-1-1.JDF
200 180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
448 V6-9 PROTON (1).ESP
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
6.0010.742.104.352.172.20
448 V6-9 CARBON (1).ESP
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
450 V7-9 PROTON.ESP
9 8 7 6 5 4 3 2 1 0 -1
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
5.869.292.062.072.081.061.972.00
450 V7-9 CARBON.ESP
200 180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
R3682AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
1.981.930.932.030.952.002.01
R3696AKC_CARBON-1-1.JDF
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
R3698AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
2.031.951.352.000.951.952.00
R3698AKC_CARBON-1-1.JDF
200 180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
R4621AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
6.092.200.952.050.952.012.00
R4658AKC_CARBON-1-1.JDF
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
R4699AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
2.012.322.232.110.972.000.971.962.00
R4703AKC_CARBON-1-1.JDF
200 180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
P6857AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
3.033.132.001.051.021.041.050.97
P6857AKC_CARBON-1-1.JDF
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
R3944AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
2.051.890.802.000.941.880.950.95
R3944AKC_CARBON-1-1.JDF
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
R3996AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
2.072.071.141.000.980.941.910.971.04
R3996AKC_CARBON-1-1.JDF
200 180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
P8627AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
2.000.941.961.962.030.822.18
P8686AKC_CARBON-1-1.JDF
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
R4464AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
1.031.000.991.990.986.33
P8970AKC_CARBON-1-1.JDF
200 180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
R0325AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
2.991.970.933.911.901.96
R0325AKC_CARBON-1-1.JDF
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
R0731AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
1.000.973.130.971.981.012.103.31
R0749AKC_CARBON-1-1.JDF
200 180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
R0326AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
2.000.962.092.031.992.01
R0326AKC_CARBON-1-1.JDF
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
R0750AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
1.000.990.972.000.991.993.12
R0750AKC_CARBON-1-1.JDF
200 180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
R4928AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
9.232.000.961.984.861.030.981.05
R4928AKC_CARBON-1-1.JDF
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
R5000AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
8.842.002.020.992.152.261.051.001.00
R5000AKC_CARBON-1-1.JDF
200 180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
R5903AKC_PROTON-1-1.JDF
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
4.072.204.441.091.091.001.061.06
R5903AKC_CARBON-1-1.JDF
200 180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
455 V9-13 PROTON.ESP
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
1.001.044.131.061.041.051.911.00
455 V9-13 CARBON.ESP
200 180 160 140 120 100 80 60 40 20
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
