a b,c S1...NS 12 DS 0 SWH 7211.539 Hz FIDRES 0.220079 Hz AQ 2.2719147 sec RG 99.72 DW 69.333 usec DE...
29
Table S1. Optimization for the Heck reaction of 5-iodouracil (3) with glycal 4 entry a aryl iodide Pd catalyst (0.1 equiv) phosphine ligand (0.2 equiv) base (1.5 equiv) yield (%) b,c 1 S1 Pd(OAc) 2 PPh 3 Et 3 N 44 (22) 2 S1 Pd(OAc) 2 XantPhos Et 3 N N.R. 3 S1 Pd(OAc) 2 DPPF Et 3 N N.R. 4 S1 Pd(OAc) 2 DPPE Et 3 N 38 (13) 5 S1 Pd 2 dba 3 PPh 3 Et 3 N 69 6 S1 Pd 2 dba 3 XantPhos Et 3 N 83 7 S1 Pd 2 dba 3 DPPF Et 3 N 62 8 S1 Pd 2 dba 3 DPPE Et 3 N N.R. 9 S1 Pd(PPh 3 ) 4 ----- Et 3 N 36 10 3 Pd(OAc) 2 PPh 3 Et 3 N 33 (6) 11 3 Pd 2 dba 3 PPh 3 Et 3 N 35 12 3 Pd 2 dba 3 XantPhos Et 3 N 35 (2) 13 3 Pd 2 dba 3 XantPhos DIPEA 65 14 3 Pd 2 dba 3 XantPhos DBU N.R. 15 3 Pd 2 dba 3 XantPhos DABCO N.R. 16 3 Pd 2 dba 3 XantPhos n-Bu 3 N 83 a reagents and conditions: glycal 4 (1.0 equiv), aryl iodide (3 or S1: 2.0 equiv), catalyst (0.1 equiv), ligand (0.2 equiv), base (1.5 equiv), reaction concentration = 0.1 M. The reactions were conducted on 0.5 mmol scale; b Isolated yield (5 or S2, respectively); c Numbers in parentheses represent the yield of the ketone product (6 or S3, respectively) Table S2. Optimization for the Heck reaction of 2,4-dimethoxy-5-iodopyrimidine (8) with glycal 4 entry a aryl iodide Pd catalyst (0.1 equiv) phosphine ligand (0.2 equiv) base (1.5 equiv) yield (%) b,c 1 8 Pd(OAc) 2 PPh 3 Et 3 N 7 (83) 2 8 Pd 2 dba 3 PPh 3 Et 3 N 77 (trace) 3 8 Pd 2 dba 3 XantPhos Et 3 N trace 4 8 Pd 2 dba 3 PPh 3 n-Bu 3 N 76 (trace) 5 8 Pd 2 dba 3 XantPhos n-Bu 3 N trace 6 8 Pd(OAc) 2 XantPhos Et 3 N 6 (71) 7 8 Pd 2 dba 3 PPh 3 Ag 2 CO 3 N.R. a reagents and conditions: glycal 4 (1.0 equiv), aryl iodide 8 (2.0 equiv), catalyst (0.1 equiv), ligand (0.2 equiv), base (1.5 equiv), reaction concentration = 0.1 M. The reactions were conducted on 0.5 mmol scale; b Isolated yield (9); c Numbers in parentheses represent the yield of the ketone product 10 Electronic Supplementary Material (ESI) for New Journal of Chemistry. This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019
Transcript of a b,c S1...NS 12 DS 0 SWH 7211.539 Hz FIDRES 0.220079 Hz AQ 2.2719147 sec RG 99.72 DW 69.333 usec DE...
Table S1. Optimization for the Heck reaction of 5-iodouracil (3) with glycal 4
entrya aryl iodide Pd catalyst (0.1 equiv) phosphine ligand (0.2 equiv) base (1.5 equiv) yield (%)b,c
1 S1 Pd(OAc)2 PPh3 Et3N 44 (22) 2 S1 Pd(OAc)2 XantPhos Et3N N.R. 3 S1 Pd(OAc)2 DPPF Et3N N.R. 4 S1 Pd(OAc)2 DPPE Et3N 38 (13) 5 S1 Pd2dba3 PPh3 Et3N 69 6 S1 Pd2dba3 XantPhos Et3N 83 7 S1 Pd2dba3 DPPF Et3N 62 8 S1 Pd2dba3 DPPE Et3N N.R. 9 S1 Pd(PPh3)4 ----- Et3N 36
10 3 Pd(OAc)2 PPh3 Et3N 33 (6) 11 3 Pd2dba3 PPh3 Et3N 35 12 3 Pd2dba3 XantPhos Et3N 35 (2) 13 3 Pd2dba3 XantPhos DIPEA 65 14 3 Pd2dba3 XantPhos DBU N.R. 15 3 Pd2dba3 XantPhos DABCO N.R. 16 3 Pd2dba3 XantPhos n-Bu3N 83
a reagents and conditions: glycal 4 (1.0 equiv), aryl iodide (3 or S1: 2.0 equiv), catalyst (0.1 equiv), ligand (0.2 equiv), base (1.5 equiv), reaction concentration = 0.1 M. The reactions were conducted on 0.5 mmol scale; b Isolated yield (5 or S2, respectively); c Numbers in parentheses represent the yield of the ketone product (6 or S3, respectively) Table S2. Optimization for the Heck reaction of 2,4-dimethoxy-5-iodopyrimidine (8) with glycal 4
entrya aryl iodide Pd catalyst (0.1 equiv) phosphine ligand (0.2 equiv) base (1.5 equiv) yield (%)b,c
1 8 Pd(OAc)2 PPh3 Et3N 7 (83) 2 8 Pd2dba3 PPh3 Et3N 77 (trace) 3 8 Pd2dba3 XantPhos Et3N trace 4 8 Pd2dba3 PPh3 n-Bu3N 76 (trace) 5 8 Pd2dba3 XantPhos n-Bu3N trace 6 8 Pd(OAc)2 XantPhos Et3N 6 (71) 7 8 Pd2dba3 PPh3 Ag2CO3 N.R.
a reagents and conditions: glycal 4 (1.0 equiv), aryl iodide 8 (2.0 equiv), catalyst (0.1 equiv), ligand (0.2 equiv), base (1.5 equiv), reaction concentration = 0.1 M. The reactions were conducted on 0.5 mmol scale; b Isolated yield (9); c Numbers in parentheses represent the yield of the ketone product 10
Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019
10 9 8 7 6 5 4 3 2 1 0 ppm
0.033
0.053
0.177
0.205
0.866
0.920
3.713
3.720
3.741
3.748
3.834
3.838
3.862
3.867
4.509
4.901
5.680
5.684
5.689
7.260
7.680
9.232
9.338
3.109
3.117
3.117
3.077
10.729
10.719
1.103
1.124
1.085
1.060
1.075
0.917
1.000
1.182
Current Data ParametersNAME TD003-1EXPNO 2PROCNO 1
F2 - Acquisition ParametersDate_ 20151222Time 22.19INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 32768SOLVENT CDCl3NS 12DS 0SWH 7211.539 HzFIDRES 0.220079 HzAQ 2.2719147 secRG 99.72DW 69.333 usecDE 10.50 usecTE 297.6 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========SFO1 400.1324008 MHzNUC1 1HP1 12.90 usecPLW1 15.00000000 W
F2 - Processing parametersSI 16384SF 400.1300098 MHzWDW EMSSB 0LB 0 HzGB 0PC 1.00
1H
OTBSO
TBSO
NHHN
O
O
3-10b
200 180 160 140 120 100 80 60 40 20 0 ppm
-5.359
-5.321
-5.151
-4.809
18.001
18.479
25.546
25.924
63.206
76.683
77.000
77.318
83.765
100.544
116.633
138.319
150.074
152.103
163.190
Current Data ParametersNAME TD003-1EXPNO 4PROCNO 1
F2 - Acquisition ParametersDate_ 20151223Time 0.02INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 32768SOLVENT CDCl3NS 2000DS 0SWH 24038.461 HzFIDRES 0.733596 HzAQ 0.6815744 secRG 198.09DW 20.800 usecDE 6.50 usecTE 298.8 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========SFO1 100.6233319 MHzNUC1 13CP1 10.00 usecPLW1 47.50000000 W
======== CHANNEL f2 ========SFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 90.00 usecPLW2 15.00000000 WPLW12 0.33750001 WPLW13 0.27338001 W
F2 - Processing parametersSI 32768SF 100.6127704 MHzWDW EMSSB 0LB 2.00 HzGB 0PC 1.00
13C
OTBSO
TBSO
NHHN
O
O
3-10b
11 10 9 8 7 6 5 4 3 2 1 ppm
2.342
2.367
2.387
2.412
2.491
2.495
2.500
2.504
2.651
2.667
2.696
2.712
3.329
3.646
3.919
3.926
3.934
4.910
4.977
4.993
5.002
5.018
7.606
11.128
11.146
11.182
1.004
3.931
0.999
7.998
2.285
1.002
0.872
1.072
1.000
1.404
Current Data ParametersNAME TD031EXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20160713Time 23.16INSTRUM spectPROBHD 5 mm BBO BB-1HPULPROG zg30TD 32768SOLVENT DMSONS 1DS 0SWH 7246.377 HzFIDRES 0.221142 HzAQ 2.2609921 secRG 256DW 69.000 usecDE 6.50 usecTE 297.2 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.40 usecPL1 1.80 dBSFO1 400.1324008 MHz
F2 - Processing parametersSI 16384SF 400.1300027 MHzWDW EMSSB 0LB 0 HzGB 0PC 1.00
1H
OHO
NHHN
O
O
3-9bO
200 180 160 140 120 100 80 60 40 20 ppm
38.872
39.081
39.290
39.499
39.707
39.916
40.125
42.683
60.605
70.590
82.059
111.774
139.301
151.108
163.467
214.182
Current Data ParametersNAME TD031EXPNO 3PROCNO 1
F2 - Acquisition ParametersDate_ 20160713Time 23.58INSTRUM spectPROBHD 5 mm BBO BB-1HPULPROG zgpg30TD 32768SOLVENT DMSONS 2000DS 0SWH 24038.461 HzFIDRES 0.733596 HzAQ 0.6815744 secRG 8192DW 20.800 usecDE 6.50 usecTE 297.5 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.00 usecPL1 7.00 dBSFO1 100.6233325 MHz
======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 90.00 usecPL2 1.80 dBPL12 17.00 dBPL13 20.00 dBSFO2 400.1316005 MHz
F2 - Processing parametersSI 32768SF 100.6128194 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.00
13C
OHO
NHHN
O
O
3-9bO
11 10 9 8 7 6 5 4 3 2 1 ppm
1.724
1.731
1.738
1.745
1.755
1.770
1.975
1.979
1.989
1.994
2.006
2.011
2.021
2.025
2.496
2.500
2.503
3.369
3.658
3.664
3.669
3.675
3.687
4.105
4.110
4.747
4.761
4.776
4.786
4.800
4.990
4.999
7.366
10.957
10.964
1.047
1.000
4.458
2.525
1.053
1.079
2.042
1.004
0.999
1.763
Current Data ParametersNAME TD010EXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20160115Time 20.54INSTRUM spectPROBHD 5 mm BBO BB-1HPULPROG zg30TD 32768SOLVENT DMSONS 12DS 0SWH 7246.377 HzFIDRES 0.221142 HzAQ 2.2609921 secRG 228.1DW 69.000 usecDE 6.50 usecTE 297.5 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.40 usecPL1 1.80 dBSFO1 400.1324008 MHz
F2 - Processing parametersSI 16384SF 400.1300030 MHzWDW EMSSB 0LB 0 HzGB 0PC 1.00
1H
OHO
NHHN
O
O
OH3-25b
200 180 160 140 120 100 80 60 40 20 ppm
38.873
39.082
39.291
39.500
39.709
39.917
40.126
40.862
62.226
72.121
73.195
87.060
113.215
137.853
151.218
163.544
Current Data ParametersNAME TD010EXPNO 6PROCNO 1
F2 - Acquisition ParametersDate_ 20160121Time 1.20INSTRUM spectPROBHD 5 mm BBO BB-1HPULPROG zgpg30TD 32768SOLVENT DMSONS 3000DS 0SWH 24038.461 HzFIDRES 0.733596 HzAQ 0.6815744 secRG 8192DW 20.800 usecDE 6.50 usecTE 298.3 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.00 usecPL1 7.00 dBSFO1 100.6233325 MHz
======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 90.00 usecPL2 1.80 dBPL12 17.00 dBPL13 20.00 dBSFO2 400.1316005 MHz
F2 - Processing parametersSI 32768SF 100.6128092 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.00
13C
OHO
NHHN
O
O
OH3-25b
10 9 8 7 6 5 4 3 2 1 0 ppm
-0.009
0.197
0.215
0.831
0.929
3.677
3.687
3.705
3.715
3.804
3.810
3.832
3.838
3.959
3.983
4.530
4.536
4.540
4.545
4.549
4.554
4.559
4.769
4.774
4.778
5.868
5.871
5.876
5.880
7.260
8.377
6.162
6.150
9.461
9.363
1.048
1.064
3.104
3.123
1.034
1.031
1.012
1.000
Current Data ParametersNAME TQ111EXPNO 101PROCNO 1
F2 - Acquisition ParametersDate_ 20161231Time 17.19INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 32768SOLVENT CDCl3NS 16DS 0SWH 7211.539 HzFIDRES 0.220079 HzAQ 2.2719147 secRG 45.15DW 69.333 usecDE 10.50 usecTE 297.8 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========SFO1 400.1324008 MHzNUC1 1HP1 12.90 usecPLW1 15.00000000 W
F2 - Processing parametersSI 16384SF 400.1300099 MHzWDW EMSSB 0LB 0 HzGB 0PC 1.00
1H of P data
OTBSO
NN
OMe
TBSO4-18
OMe
200 180 160 140 120 100 80 60 40 20 0 ppm
-5.6
0-5
.54
-5.1
3
17.8
218
.34
25.3
425
.81
53.6
254
.40
63.8
0
76.7
6
83.9
2
99.3
3
116.
28
151.
0415
7.29
164.
5316
8.22
Current Data ParametersNAME TQ111EXPNO 105PROCNO 1
F2 - Acquisition ParametersDate_ 20161231Time 17.31INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 32768SOLVENT CDCl3NS 59DS 0SWH 24038.461 HzFIDRES 0.733596 HzAQ 0.6815744 secRG 198.09DW 20.800 usecDE 6.50 usecTE 298.2 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========SFO1 100.6228298 MHzNUC1 13CP1 10.00 usecPLW1 47.50000000 W
======== CHANNEL f2 ========SFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 90.00 usecPLW2 15.00000000 WPLW12 0.33750001 WPLW13 0.27338001 W
F2 - Processing parametersSI 32768SF 100.6127817 MHzWDW EMSSB 0LB 2.00 HzGB 0PC 1.00
13C of P data
OTBSO
NN
OMe
TBSO4-18
OMe
10 9 8 7 6 5 4 3 2 1 0 ppm
0.021
0.040
0.820
2.254
2.281
2.298
2.325
2.830
2.845
2.874
2.890
3.884
3.893
3.913
3.921
3.928
3.934
3.956
3.962
3.970
3.976
3.986
3.993
5.213
5.227
5.240
5.255
7.260
8.480
6.191
9.359
1.060
1.053
1.977
7.258
1.033
1.000
Current Data ParametersNAME TQ115EXPNO 101PROCNO 1
F2 - Acquisition ParametersDate_ 20170101Time 21.51INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 32768SOLVENT CDCl3NS 16DS 0SWH 7211.539 HzFIDRES 0.220079 HzAQ 2.2719147 secRG 45.15DW 69.333 usecDE 10.50 usecTE 297.6 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========SFO1 400.1324008 MHzNUC1 1HP1 12.90 usecPLW1 15.00000000 W
F2 - Processing parametersSI 16384SF 400.1300097 MHzWDW EMSSB 0LB 0 HzGB 0PC 1.00
1H of P data
4-19
OTBSO
NN
OMe
OMe
O
200 180 160 140 120 100 80 60 40 20 0 ppm
-5.6
9-5
.46
18.1
8
25.7
3
44.2
6
53.9
554
.79
62.5
1
70.8
0
82.4
4
114.
52
155.
72
164.
9416
8.04
213.
37
Current Data ParametersNAME TQ115EXPNO 103PROCNO 1
F2 - Acquisition ParametersDate_ 20170101Time 21.56INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 32768SOLVENT CDCl3NS 201DS 0SWH 24038.461 HzFIDRES 0.733596 HzAQ 0.6815744 secRG 198.09DW 20.800 usecDE 6.50 usecTE 298.1 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========SFO1 100.6228298 MHzNUC1 13CP1 10.00 usecPLW1 47.50000000 W
======== CHANNEL f2 ========SFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 90.00 usecPLW2 15.00000000 WPLW12 0.33750001 WPLW13 0.27338001 W
F2 - Processing parametersSI 32768SF 100.6127736 MHzWDW EMSSB 0LB 2.00 HzGB 0PC 1.00
13C of P data
4-19
OTBSO
NN
OMe
OMe
O
Current Data ParametersNAME TQ133EXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20170213Time 16.42INSTRUM spectPROBHD 5 mm BBO BB-1HPULPROG zg30TD 32768SOLVENT CDCl3NS 1DS 0SWH 7246.377 HzFIDRES 0.221142 HzAQ 2.2609921 secRG 71.8DW 69.000 usecDE 6.50 usecTE 296.8 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.40 usecPL1 1.80 dBSFO1 400.1324008 MHz
F2 - Processing parametersSI 16384SF 400.1300091 MHzWDW EMSSB 0LB 0 HzGB 0PC 1.00
1H of P 25-30
10 9 8 7 6 5 4 3 2 1 ppm
2.5036
2.5305
2.5488
2.5757
2.7791
2.7945
2.8244
2.8396
3.8694
3.8807
3.8884
3.9475
3.9698
3.9856
3.9924
5.1797
5.1951
5.2063
5.2218
7.2601
8.3441
1.1048
1.0622
9.2921
0.9942
1.0000
200 180 160 140 120 100 80 60 40 20 ppm
43.029
54.070
54.854
61.343
71.912
81.966
113.365
156.402
165.094
168.332
213.497
Current Data ParametersNAME TQ133EXPNO 3PROCNO 1
F2 - Acquisition ParametersDate_ 20170213Time 16.48INSTRUM spectPROBHD 5 mm BBO BB-1HPULPROG zgpg30TD 32768SOLVENT CDCl3NS 262DS 0SWH 24038.461 HzFIDRES 0.733596 HzAQ 0.6815744 secRG 8192DW 20.800 usecDE 6.50 usecTE 297.1 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.00 usecPL1 7.00 dBSFO1 100.6233325 MHz
======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 90.00 usecPL2 1.80 dBPL12 17.00 dBPL13 20.00 dBSFO2 400.1316005 MHz
F2 - Processing parametersSI 32768SF 100.6127797 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.00
10 9 8 7 6 5 4 3 2 1 0 ppm
0.995
2.400
2.428
2.444
2.471
2.917
2.932
2.961
2.975
3.978
3.993
3.998
4.008
4.020
4.038
4.044
5.244
5.259
5.272
5.286
7.260
7.364
7.381
7.398
7.415
7.423
7.427
7.440
7.648
7.664
7.699
7.714
8.541
9.133
1.015
1.041
3.324
1.989
2.953
1.145
1.012
6.269
4.196
1.000
Current Data ParametersNAME TQ160EXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20170317Time 19.48INSTRUM spectPROBHD 5 mm BBO BB-1HPULPROG zg30TD 32768SOLVENT CDCl3NS 16DS 0SWH 7246.377 HzFIDRES 0.221142 HzAQ 2.2609921 secRG 228.1DW 69.000 usecDE 6.50 usecTE 298.3 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.40 usecPL1 1.80 dBSFO1 400.1324008 MHz
F2 - Processing parametersSI 16384SF 400.1300091 MHzWDW EMSSB 0LB 0 HzGB 0PC 1.00
1H of P data
4-25
OTBDPSO
NN
OMe
OMe
O
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
19.0
8
26.5
8
44.2
7
53.9
054
.77
62.8
6
70.9
6
82.3
7
114.
2112
7.64
127.
7012
9.70
132.
5913
2.81
135.
4413
5.52
155.
59
164.
9516
8.04
213.
17
Current Data ParametersNAME TQ160EXPNO 4PROCNO 1
F2 - Acquisition ParametersDate_ 20170317Time 19.57INSTRUM spectPROBHD 5 mm BBO BB-1HPULPROG zgpg30TD 32768SOLVENT CDCl3NS 81DS 0SWH 24038.461 HzFIDRES 0.733596 HzAQ 0.6815744 secRG 4096DW 20.800 usecDE 6.50 usecTE 298.5 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.00 usecPL1 7.00 dBSFO1 100.6233325 MHz
======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 90.00 usecPL2 1.80 dBPL12 17.00 dBPL13 20.00 dBSFO2 400.1316005 MHz
F2 - Processing parametersSI 32768SF 100.6127690 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.00
13C of P data
4-25
OTBDPSO
NN
OMe
OMe
O
10 9 8 7 6 5 4 3 2 1 0 ppm
1.054
1.066
1.900
1.924
1.933
1.958
2.652
3.914
3.918
3.925
3.929
3.940
3.946
3.969
3.974
3.979
4.027
4.054
4.064
4.087
4.102
4.114
4.955
4.974
4.992
7.260
7.378
7.383
7.394
7.398
7.400
7.403
7.412
7.413
7.418
7.423
7.427
7.431
7.434
7.438
7.445
7.447
7.673
7.677
7.693
7.696
7.705
7.709
7.714
7.722
7.725
7.729
1.869
9.107
0.994
1.236
0.177
1.040
0.968
0.205
0.201
1.082
0.558
6.783
0.156
1.061
1.051
0.183
1.031
1.026
0.175
7.286
4.872
0.179
1.000
Current Data ParametersNAME TQ161EXPNO 101PROCNO 1
F2 - Acquisition ParametersDate_ 20170318Time 16.42INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 32768SOLVENT CDCl3NS 16DS 0SWH 7211.539 HzFIDRES 0.220079 HzAQ 2.2719147 secRG 89.08DW 69.333 usecDE 10.50 usecTE 298.3 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========SFO1 400.1324008 MHzNUC1 1HP1 12.90 usecPLW1 15.00000000 W
F2 - Processing parametersSI 16384SF 400.1300099 MHzWDW EMSSB 0LB 0 HzGB 0PC 1.00
1H of P data
4-26
OTBDPSO
NN
OMe
OMe
HO
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
18.9
119
.01
26.6
3
41.2
441
.57
53.5
653
.67
54.4
862
.75
64.4
272
.60
73.1
173
.28
73.5
977
.19
81.6
986
.86
115.
2811
5.84
127.
5712
7.66
129.
6012
9.74
132.
4813
2.62
132.
9613
3.01
135.
3615
5.22
155.
7316
4.42
164.
4716
7.66
167.
94
Current Data ParametersNAME TQ161EXPNO 104PROCNO 1
F2 - Acquisition ParametersDate_ 20170318Time 16.55INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 32768SOLVENT CDCl3NS 793DS 0SWH 24038.461 HzFIDRES 0.733596 HzAQ 0.6815744 secRG 198.09DW 20.800 usecDE 6.50 usecTE 298.8 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========SFO1 100.6228298 MHzNUC1 13CP1 10.00 usecPLW1 47.50000000 W
======== CHANNEL f2 ========SFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 90.00 usecPLW2 15.00000000 WPLW12 0.33750001 WPLW13 0.27338001 W
F2 - Processing parametersSI 32768SF 100.6127905 MHzWDW EMSSB 0LB 2.00 HzGB 0PC 1.00
13C of P data
4-26
OTBDPSO
NN
OMe
OMe
HO
10 9 8 7 6 5 4 3 2 1 0 ppm
3.610
3.622
3.640
3.651
3.716
3.724
3.745
3.753
3.939
3.977
4.946
4.957
4.960
4.963
4.965
4.968
4.971
4.974
4.986
5.853
5.856
5.862
5.867
5.871
5.901
5.905
5.907
5.910
5.916
5.920
5.922
5.926
5.956
5.960
5.965
5.971
5.976
5.981
7.260
8.199
1.059
1.065
6.313
1.008
0.966
0.995
1.002
1.000
Current Data ParametersNAME TQ167EXPNO 110PROCNO 1
F2 - Acquisition ParametersDate_ 20170331Time 3.29INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 32768SOLVENT CDCl3NS 16DS 0SWH 7211.539 HzFIDRES 0.220079 HzAQ 2.2719147 secRG 57.42DW 69.333 usecDE 10.50 usecTE 298.2 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========SFO1 400.1324008 MHzNUC1 1HP1 12.90 usecPLW1 15.00000000 W
F2 - Processing parametersSI 16384SF 400.1300097 MHzWDW EMSSB 0LB 0 HzGB 0PC 1.00
1H of P data
4-21
OHO
NN
OMe
OMe
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
53.9
854
.75
64.7
4
80.7
587
.22
114.
84
128.
1312
9.81
156.
67
164.
9016
8.51
Current Data ParametersNAME TQ167EXPNO 109PROCNO 1
F2 - Acquisition ParametersDate_ 20170331Time 3.27INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 32768SOLVENT CDCl3NS 1000DS 0SWH 24038.461 HzFIDRES 0.733596 HzAQ 0.6815744 secRG 198.09DW 20.800 usecDE 6.50 usecTE 298.9 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========SFO1 100.6228298 MHzNUC1 13CP1 10.00 usecPLW1 47.50000000 W
======== CHANNEL f2 ========SFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 90.00 usecPLW2 15.00000000 WPLW12 0.33750001 WPLW13 0.27338001 W
F2 - Processing parametersSI 32768SF 100.6127766 MHzWDW EMSSB 0LB 2.00 HzGB 0PC 1.00
13C of P data
4-21
OHO
NN
OMe
OMe
10 9 8 7 6 5 4 3 2 1 0 ppm
3.768
3.779
3.793
3.804
3.890
3.896
3.914
3.921
3.951
3.994
4.029
4.036
4.041
4.048
4.052
4.059
4.131
4.142
4.154
4.237
4.248
4.258
4.790
4.888
4.898
8.243
1.031
1.070
2.994
2.902
1.056
0.993
0.990
1.001
1.000
Current Data ParametersNAME TCC-2017030185EXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20170330Time 16.40INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT D2ONS 64DS 0SWH 6510.417 HzFIDRES 0.099341 HzAQ 5.0331650 secRG 35.9DW 76.800 usecDE 6.50 usecTE 300.0 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.30 usecPL1 -0.50 dBSFO1 500.1322506 MHz
F2 - Processing parametersSI 65536SF 500.1299561 MHzWDW EMSSB 0LB 0.10 HzGB 0PC 1.00
1H of TQ170 P2 data
4-27
OHO
NN
OMe
OMe
HO OH
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
54.3
055
.00
61.3
9
70.6
474
.45
78.7
582
.99
112.
86
155.
65
164.
6616
8.91
Current Data ParametersNAME TCC-2017030185EXPNO 6PROCNO 1
F2 - Acquisition ParametersDate_ 20170331Time 2.06INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT D2ONS 400DS 0SWH 30303.031 HzFIDRES 0.462388 HzAQ 1.0813440 secRG 5792.6DW 16.500 usecDE 6.50 usecTE 300.0 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 10.10 usecPL1 6.00 dBSFO1 125.7709936 MHz
======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -0.50 dBPL12 16.00 dBPL13 19.00 dBSFO2 500.1320005 MHz
F2 - Processing parametersSI 65536SF 125.7577890 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.00
13C of TQ170 P2 data
4-27
OHO
NN
OMe
OMe
HO OH
10 9 8 7 6 5 4 3 2 1 0 ppm3.792
3.806
3.822
3.837
3.869
3.877
3.899
3.908
3.949
3.960
4.184
4.194
4.200
4.210
4.215
4.225
4.424
4.436
4.447
4.618
4.632
4.648
4.790
5.010
5.020
8.253
1.148
1.157
3.108
3.204
1.066
1.087
1.072
1.047
1.000
Current Data ParametersNAME TQ170EXPNO 102PROCNO 1
F2 - Acquisition ParametersDate_ 20170419Time 13.13INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 32768SOLVENT D2ONS 16DS 0SWH 7211.539 HzFIDRES 0.220079 HzAQ 2.2719147 secRG 36.64DW 69.333 usecDE 10.50 usecTE 298.1 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========SFO1 400.1324008 MHzNUC1 1HP1 12.90 usecPLW1 15.00000000 W
F2 - Processing parametersSI 16384SF 400.1299654 MHzWDW EMSSB 0LB 0 HzGB 0PC 1.00
1H of P1 data
4-27 cis
OHO
NN
OMe
OMe
HO OH
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
54.3
054
.93
60.4
071
.11
71.9
675
.62
79.4
4
111.
54
155.
53
164.
3816
8.16
Current Data ParametersNAME TQ170EXPNO 104PROCNO 1
F2 - Acquisition ParametersDate_ 20170419Time 13.19INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 32768SOLVENT D2ONS 100DS 0SWH 24038.461 HzFIDRES 0.733596 HzAQ 0.6815744 secRG 198.09DW 20.800 usecDE 6.50 usecTE 298.5 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========SFO1 100.6228298 MHzNUC1 13CP1 10.00 usecPLW1 47.50000000 W
======== CHANNEL f2 ========SFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 90.00 usecPLW2 15.00000000 WPLW12 0.33750001 WPLW13 0.27338001 W
F2 - Processing parametersSI 32768SF 100.6127685 MHzWDW EMSSB 0LB 2.00 HzGB 0PC 1.00
13C of P1 data
4-27 cis
OHO
NN
OMe
OMe
HO OH
10 9 8 7 6 5 4 3 2 1 0 ppm
2.497
2.500
2.504
3.427
3.434
3.450
3.458
3.573
3.579
3.596
3.603
3.679
3.686
3.691
3.697
3.704
3.849
3.859
3.870
3.907
3.916
3.926
4.452
4.462
7.516
1.370
1.333
1.174
1.101
1.100
1.135
1.000
Current Data ParametersNAME TCC-2017040199EXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20170407Time 16.59INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT DMSONS 128DS 0SWH 8012.820 HzFIDRES 0.122266 HzAQ 4.0894465 secRG 128DW 62.400 usecDE 6.50 usecTE 300.1 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.30 usecPL1 -0.50 dBSFO1 500.1335009 MHz
F2 - Processing parametersSI 65536SF 500.1300045 MHzWDW EMSSB 0LB 0 HzGB 0PC 1.00
1H of TQ172 P data
Pseudouridine (1-1)
OHO
HO OH
NHHN
O
O
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
61.1
6
70.4
273
.85
78.9
083
.20
110.
99
140.
12
151.
31
163.
72
Current Data ParametersNAME TCC-2017040199EXPNO 6PROCNO 1
F2 - Acquisition ParametersDate_ 20170408Time 8.02INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT DMSONS 3000DS 0SWH 30303.031 HzFIDRES 0.462388 HzAQ 1.0813440 secRG 8192DW 16.500 usecDE 6.50 usecTE 300.5 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 10.10 usecPL1 6.00 dBSFO1 125.7709936 MHz
======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -0.50 dBPL12 16.00 dBPL13 19.00 dBSFO2 500.1320005 MHz
F2 - Processing parametersSI 65536SF 125.7578470 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.00
13C of TQ172 P data
Pseudouridine (1-1)
OHO
HO OH
NHHN
O
O
10 9 8 7 6 5 4 3 2 1 0 ppm
3.720
3.767
3.776
3.792
3.801
3.883
3.889
3.908
3.914
4.063
4.069
4.073
4.080
4.083
4.090
4.192
4.203
4.214
4.335
4.346
4.356
4.733
4.744
4.790
7.725
7.726
1.070
1.019
1.040
1.013
1.012
1.283
1.000
Current Data ParametersNAME TCC-2017040198EXPNO 11PROCNO 1
F2 - Acquisition ParametersDate_ 20170420Time 8.48INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 32768SOLVENT D2ONS 128DS 0SWH 6510.417 HzFIDRES 0.198682 HzAQ 2.5165825 secRG 128DW 76.800 usecDE 6.50 usecTE 300.0 KD1 2.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.30 usecPL1 -0.50 dBSFO1 500.1322506 MHz
F2 - Processing parametersSI 32768SF 500.1299558 MHzWDW EMSSB 0LB 0 HzGB 0PC 1.00
1H of TQ172 P data
Pseudouridine (1-1)
OHO
HO OH
NHHN
O
O
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
61.5
4
70.8
573
.38
79.1
283
.38
110.
50
141.
60
152.
87
165.
35
Current Data ParametersNAME TCC-2017040198EXPNO 6PROCNO 1
F2 - Acquisition ParametersDate_ 20170420Time 6.18INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT D2ONS 4000DS 0SWH 30303.031 HzFIDRES 0.462388 HzAQ 1.0813440 secRG 8192DW 16.500 usecDE 6.50 usecTE 300.0 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 10.10 usecPL1 6.00 dBSFO1 125.7709936 MHz
======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -0.50 dBPL12 16.00 dBPL13 19.00 dBSFO2 500.1320005 MHz
F2 - Processing parametersSI 65536SF 125.7577890 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.00
13C of TQ172 P data
Pseudouridine (1-1)
OHO
HO OH
NHHN
O
O
Table S3. Spectral data comparison: 1H NMR in DMSO-d6 (δ, ppm)
peak (1H, δ)
Smitha Noyorib (100 MHz)
This work (500 MHz)
1 7.546 (s, 1H, H-6) 7.52 (d, J = 6.0 Hz, 1H, H-6) 7.52 (s, 1H, H-6) 2 4.471 (J = 4.5 Hz,1H, H-1’) 4.51 (d, J = 4.0 Hz, 1H, H-1’) 4.46 (d, J = 4.5 Hz,1H, H-1’) 3 3.925 (J = 4.5 Hz, 1H, H-2’) 3.3-4.0 (m, 5H, H-2’, H-3’, H-4’,
H-5’) 3.92 (t, J = 4.8 Hz, 1H, H-2’)
4 3.877 (J = 5.3, 4.5 Hz, 1H, H-3’) ----- 3.86 (t, J = 5.3 Hz, 1H, H-3’) 5 3.706 (J = 5.3, 3.5, 3.0 Hz, 1H,
H-4’) ----- 3.69 (dt, J = 5.5, 3.2 Hz, 1H,
H-4’) 6 3.601 (dd, J = 11.9, 3.0 Hz, 1H,
H-5’) ----- 3.59 (dd, J = 11.9, 3.1 Hz, 1H,
H-5a’) 7 3.450 (dd, J = 11.9, 3.5 Hz, 1H,
H-5’) ----- 3.44 (dd, J = 11.9, 3.7 Hz, 1H,
H-5’) 8 4.855 (d, J = 4.8 Hz, 1H, OH),
4.743 (dd, J = 6.2, 4.8 Hz, 1H, OH),
4.655 (d, J = 5.3 Hz, 1H, OH)
11.07 (br s, 1H, H-3), 10.85 (d, J = 6.0 Hz, 1H, H-1),
4.54 (br s, 3H, 3 OH)
-----
a Deslauriers, R.; Smith, I. C. P. Can. J. Chem. 1973, 51 833; b Sato, T.; Hayakawa, Y.; Noyori, R. Bull. Chem. Soc. Jpn. 1984, 57, 2515 Table S4. Spectral data comparison: 13C NMR in DMSO-d6 (δ, ppm)
peak (13C, δ)
Wenkerta (15 MHz)
Townsendb (25 MHz)
Noyoric (20 MHz)
This workd (125 MHz)
1 164.8 (C-4) 163.95 (C-4) 163.57 163.7 2 152.3 (C-2) 151.36 (C-2) 150.98 151.3 3 141.0 (C-6) 140.14 (C-6) 139.62 140.1 (CH) 4 110.0 (C-5) 111.27 (C-5) 111.05 111.0 5 82.9 (C-4’) 83.60 (C-4’) 83.47 83.2 (CH) 6 78.6 (C-1’) 79.13 (C-1’) 78.88 78.9 (CH) 7 72.9 (C-2’) 74.10 (C-2’) 73.93 73.9 (CH) 8 71.3 (C-3’) 70.80 (C-3’) 70.62 70.4 (CH) 9 61.1 (C-5’) 61.55 (C-5’) 61.36 61.2 (CH2)
a Wenkert, B.; Hagaman, E. W.; Gutowski, G. E.; Biochem. Biophys. Res. Commun. 1973, 51, 318; b Chenon, M.-T.; Pugmire, R. L.; Grant, D. M.; Panzica, R. P.; Townsend, L. B. J. Heterocycl. Chem. 1973, 10, 427; c Sato, T.; Hayakawa, Y.; Noyori, R. Bull. Chem. Soc. Jpn. 1984, 57, 2515; d The numbers of protons directly attached to the individual carbons were determined by 13C NMR DEPT experiments
Table S5. Spectral data comparison: 1H NMR in D2O (δ, ppm)
peak (1H, δ)
Sasakia (100 MHz)
Smithb,c (100 MHz)
Chowd,e (500 MHz)
This work (500 MHz)
1 7.63 (s, 1H, H-6) 7.660 (d, J = 0.8 Hz, 1H, H-6)
7.50 (d, J = 3.0 Hz, 1H) 7.73 (d, J = 0.6 Hz, 1H, H-6)
2 4.67 (d, J = 5.0 Hz, 1H, H-1’)
4.674 (dd, J = 5.0, 0.8 Hz, 1H, H-1’)
4.51 (d, J = 5.5 Hz, 1H) 4.74 (d, J = 5.6 Hz,1H, H-1’)
3 4.27 (t, J = 5.0 Hz, 1H, H-2’)
4.279 (t, J = 5.0 Hz, 1H, H-2’)
4.13 (t, J = 5.5 Hz, 1H) 4.35 (t, J = 5.5 Hz, 1H, H-2’)
4 4.13 (t, J = 5.2 Hz, 1H, H-3’)
4.141 (t, J = 5.2 Hz, 1H, H-3’)
3.98 (t, J = 5.5 Hz, 1H) 4.20 (t, J = 5.4 Hz, 1H, H-3’)
5 4.00 (ddd, J = 5.2, 4.5, 3.5 Hz, 1H, H-4’)
4.009 (J = 5.2, 4.6, 3.2 Hz, 1H, H-4’)
3.85 (m, 1H) 4.08 (dt, J = 5.3, 3.3 Hz, 1H, H-4’)
6 3.82 (dd, J = 12.5, 3.5 Hz, 1H, H-5’)
3.840 (dd, J = 12.7, 3.2 Hz, 1H, H-5’)
3.68 (dd, J = 12.0, 3.0 Hz, 1H)
3.90 (dd, J = 12.5, 3.2 Hz, 1H, H-5’)
7 3.73 (dd, J = 12.5, 4.5 Hz, 1H, H-5’)
3.726 (dd, J = 12.7, 4.6 Hz, 1H, H-5’)
3.56 (dd, J = 13.0, 5.0 Hz, 1H)
3.78 (dd, J = 12.5, 4.9 Hz, 1H, H-5’)
a Sasaki, K.; Kusakabe, Y.; Esumi, S. J. Antibiot. 1972, 25, 151; b Frank E. Hruska, Arthur A. Grey, Ian C. P. Smith, J. Am. Chem. Soc. 1970, 92, 4088; c Deslauriers, R.; Smith, I. C. P. Can. J. Chem. 1973, 51 833; d Desaulniers, J.-P.; Chang, Y.-C.; Aduri, R.; Abeysirigunawardena, S. C.; SantaLucia J.; Chow, C. S. Org. Biomol. Chem. 2008, 6, 3892; e [1,3-15N]-pseudouridine Table S6. Spectral data comparison: 13C NMR in D2O (δ, ppm)
peak (13C, δ)
Chattopadhyayaa (125 MHz)
Chowb,c (125 MHz)
This workd (125 MHz)
1 165.7 (C-4) 165.36 165.4 2 153.2 (C-2) (141.63) 152.9 3 141.9 (C-6) 141.54 141.6 (CH) 4 110.9 (C-5) 110.59 110.5 5 ----- 83.46 83.4 (CH) 6 ----- 79.27 79.1 (CH) 7 ----- 73.45 73.4 (CH) 8 ----- 70.92 70.9 (CH) 9 ----- 61.60 61.5 (CH2)
a Luyten, I.; Pankiewicz, K. W.; Watanabe, K. A.; Chattopadhyaya, J. J. Org. Chem. 1998, 63, 1033; b Desaulniers, J.-P.; Chang, Y.-C.; Aduri, R.; Abeysirigunawardena, S. C.; SantaLucia, J.; Chow, C. S. Org. Biomol. Chem. 2008, 6, 3892; c [1,3-15N]-pseudouridine; d The numbers of protons directly attached to the individual carbons were determined by 13C NMR DEPT experiments
