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Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2009
Novel chemoenzymatic methodology for the regioselective glycine loading on polyhydroxy compounds
Shashwat Malhotra,a,b Marcelo Calderon,b Ashok K. Prasad,a Virinder S. Parmar*a and
Rainer Haag*b
aBioorganic Laboratory, Department of Chemistry, University of Delhi, Delhi 110 007, India bInstitut für Chemie und Biochemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany
Table of Contents
1. 1H-NMR, 13C-NMR and high resolution mass spectra of compounds 3, 4, 11, 13, 16, 17, 18, 19, 25 and 29.
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2009
1H NMR spectrum (Bruker DRX-400, 400 MHz, methanol-d4) of compound 3
13C NMR spectrum (Bruker DRX-400, 100.5 MHz, methanol-d4) of compound 3
solvent peakmethanol-d4solvent peak
methanol-d4
solvent peakmethanol-d4solvent peak
methanol-d4
HO
HO O
ONH
O
O1'
2'
3'
12
solvent peakmethanol-d4
HO
HO O
ONH
O
O1'
2'
3'
12
solvent peakmethanol-d4
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2009
HRMS (ESI) of compound 3
1H NMR spectrum (Bruker DRX-400, 400 MHz, methanol-d4) of compound 4
O
ONH
O
O
O
O HN
O
O
1' 2'HO
1
3
2
1' 2'
solvent peakmethanol-d4solvent peak
methanol-d4
O
ONH
O
O
O
O HN
O
O
1' 2'HO
1
3
2
1' 2'
O
ONH
O
O
O
O HN
O
O
1' 2'HO
1
3
2
1' 2'
solvent peakmethanol-d4solvent peak
methanol-d4
HO
HO O
ONH
O
O1'
2'
3'
12
HO
HO O
ONH
O
O1'
2'
3'
12
Supplementary Material (ESI) for Organic & Biomolecular Chemistry
This journal is (c) The Royal Society of Chemistry 2009
13C NMR spectrum (Bruker DRX-400, 100.5 MHz, methanol-d4) of compound 4
HRMS (ESI) of compound 4
O
ONH
O
O
O
O HN
O
O
1' 2'HO
1
3
2
1' 2'
solvent peakmethanol-d4
O
ONH
O
O
O
O HN
O
O
1' 2'HO
1
3
2
1' 2'
O
ONH
O
O
O
O HN
O
O
1' 2'HO
1
3
2
1' 2'
solvent peakmethanol-d4
O
ONH
O
O
O
O HN
O
O
1' 2'HO
1
3
2
1' 2'
O
ONH
O
O
O
O HN
O
O
1' 2'HO
1
3
2
1' 2'
Supplementary Material (ESI) for Organic & Biomolecular Chemistry
This journal is (c) The Royal Society of Chemistry 2009
1H NMR spectrum (Bruker DRX-400, 400 MHz, methanol-d4) of compound 11
13C NMR spectrum (Bruker DRX-400, 100.5 MHz, methanol-d4) of compound 11
O
O
OH
O
OH
OHN3
O HN
O
O1 21'
2'3'
1''
2''3''
1''' 2'''
3'''
solvent peakmethanol-d4
solvent peakmethanol-d4
O
O
OH
O
OH
OHN3
O HN
O
O1 21'
2'3'
1''
2''3''
1''' 2'''
3'''
solvent peakmethanol-d4
solvent peakmethanol-d4
O
O
OH
O
OH
OHN3
O HN
O
O1 21'
2'3'
1''
2''3''
1''' 2'''
3''' solvent peakmethanol-d4
O
O
OH
O
OH
OHN3
O HN
O
O1 21'
2'3'
1''
2''3''
1''' 2'''
3''' solvent peakmethanol-d4
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2009
HRMS (ESI) of compound 11
1H NMR spectrum (Bruker DRX-400, 400 MHz, methanol-d4) of compound 13
ppm (t1)0.01.02.03.04.05.06.0
0
50
100
150
200
4.22
14.
210
4.19
24.
182
4.14
64.
131
4.11
84.
102
3.94
93.
935
3.92
23.
807
3.71
73.
712
3.70
53.
701
3.68
63.
673
3.65
83.
642
3.62
83.
622
3.61
73.
612
3.60
63.
601
3.59
53.
591
3.58
03.
578
3.57
43.
564
3.55
73.
554
3.52
33.
510
1.43
1
18.00
3.82
3.865.05
1.75
1.781.81
Date:14 Jul 2009Document's Title:SG1NLU
Spectrum Title:SG1NLU MET...:12 2009 T=22.50
Frequency (MHz):(f1) 399.785 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 4.3136 Spectral Width (ppm):(f1) 19.001 Pulse Program:
Temperature:298.84Number of Scans:8Acq. Date:Thu Apr 02 04:12:13 PM
O
O
OH
O
O
OHN3
O HN
O
NH
O
O
O
O
12
2''
1' 2'3'
1' 2'3'
1''
1''
2''
3
solvent peakmethanol-d4solvent peak
methanol-d4
ppm (t1)0.01.02.03.04.05.06.0
0
50
100
150
200
4.22
14.
210
4.19
24.
182
4.14
64.
131
4.11
84.
102
3.94
93.
935
3.92
23.
807
3.71
73.
712
3.70
53.
701
3.68
63.
673
3.65
83.
642
3.62
83.
622
3.61
73.
612
3.60
63.
601
3.59
53.
591
3.58
03.
578
3.57
43.
564
3.55
73.
554
3.52
33.
510
1.43
1
18.00
3.82
3.865.05
1.75
1.781.81
Date:14 Jul 2009Document's Title:SG1NLU
Spectrum Title:SG1NLU MET...:12 2009 T=22.50
Frequency (MHz):(f1) 399.785 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 4.3136 Spectral Width (ppm):(f1) 19.001 Pulse Program:
Temperature:298.84Number of Scans:8Acq. Date:Thu Apr 02 04:12:13 PM
O
O
OH
O
O
OHN3
O HN
O
NH
O
O
O
O
12
2''
1' 2'3'
1' 2'3'
1''
1''
2''
3
solvent peakmethanol-d4solvent peak
methanol-d4
O
O
OH
O
OH
OHN3
O HN
O
O1 21'
2'3'
1''
2''3''
1''' 2'''
3'''
O
O
OH
O
OH
OHN3
O HN
O
O1 21'
2'3'
1''
2''3''
1''' 2'''
3'''
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2009
13C NMR spectrum (Bruker DRX-400, 100.5 MHz, methanol-d4) of compound 13
HRMS (ESI) of compound 13
O
O
OH
O
O
OHN3
O HN
O
NH
O
O
O
O
12
2''
1' 2'3'
1' 2'3'
1''
1''
2''
3
solvent peakmethanol-d4
O
O
OH
O
O
OHN3
O HN
O
NH
O
O
O
O
12
2''
1' 2'3'
1' 2'3'
1''
1''
2''
3
O
O
OH
O
O
OHN3
O HN
O
NH
O
O
O
O
12
2''
1' 2'3'
1' 2'3'
1''
1''
2''
3
solvent peakmethanol-d4
O
O
OH
O
O
OHN3
O HN
O
NH
O
O
O
O
12
2''
1' 2'3'
1' 2'3'
1''
1''
2''
3
O
O
OH
O
O
OHN3
O HN
O
NH
O
O
O
O
12
2''
1' 2'3'
1' 2'3'
1''
1''
2''
3
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2009
1H NMR spectrum (Bruker DRX-400, 400 MHz, methanol-d4) of compound 16
13C NMR spectrum (Bruker DRX-400, 100.5 MHz, methanol-d4) of compound 16
solvent peakmethanol-d4
solvent peakmethanol-d4
O
O
OH
O
OH
OHN
O
NN
O
OHN1''
2''3'
2'1'
1
2
3
1''' 2'''
3'''
1a
2a
3a
4a 5a1b1c18cH3C(H2C)16H2C-O-H2C
solvent peakmethanol-d4
solvent peakmethanol-d4
O
O
OH
O
OH
OHN
O
NN
O
OHN1''
2''3'
2'1'
1
2
3
1''' 2'''
3'''
1a
2a
3a
4a 5a1b1c18cH3C(H2C)16H2C-O-H2C
solvent peakmethanol-d4
O
O
OH
O
OH
OHN
O
NN
O
OHN1''
2''3'
2'1'
1
2
3
1''' 2 '''
3 '''
1a
2a
3a
4a 5a1b1c18cH3C(H2C)16H2C-O-H2C
solvent peakmethanol-d4
O
O
OH
O
OH
OHN
O
NN
O
OHN1''
2''3'
2'1'
1
2
3
1''' 2 '''
3 '''
1a
2a
3a
4a 5a1b1c18cH3C(H2C)16H2C-O-H2C
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2009
HRMS (ESI) of compound 16
1H NMR spectrum (Bruker DRX-400, 400 MHz, methanol-d4) of compound 17
O
O
OH
O
OH
OHN
O
NN
O
OHN1''
2''3'
2'1'
1
2
3
1''' 2'''
3'''
1a
2a
3a
4a 5a1b1c18cH3C(H2C)16H2C-O-H2C
O
O
OH
O
OH
OHN
O
NN
O
OHN1''
2''3'
2'1'
1
2
3
1''' 2'''
3'''
1a
2a
3a
4a 5a1b1c18cH3C(H2C)16H2C-O-H2C
solvent peakmethanol-d4
solvent peakmethanol-d4
O
O
OH
O
O
OHN
O HN
O
NH
NN
O
O
O
O
1
2
3
1'2'
3'
1'2'
3'
1'' 2''
1''2''
1a
2a3a
4a5a1b1c18c
H3C(H2C)16H2C-O-H2C
solvent peakmethanol-d4
solvent peakmethanol-d4
O
O
OH
O
O
OHN
O HN
O
NH
NN
O
O
O
O
1
2
3
1'2'
3'
1'2'
3'
1'' 2''
1''2''
1a
2a3a
4a5a1b1c18c
H3C(H2C)16H2C-O-H2C
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2009
Expansion of 1H NMR spectrum (Bruker DRX-400, 400 MHz, methanol-d4) of compound 17
13C NMR spectrum (Bruker DRX-400, 100.5 MHz, methanol-d4) of compound 17
ppm (t1)3.504.004.50
0
50
100
4.49
7
4.01
83.
998
3.97
0
3.88
93.
862
3.84
83.
844
3.72
03.
694
3.64
1
3.54
53.
523
3.43
53.
423
3.41
13.
397
3.34
7
326
6
4.26
3.73
1.17
1.67
2.19
2.00
6.18
2.04
Date:14 Jul 2009Document's Title:G1ND18
Spectrum Title:G1ND18 CD3OD 1H
Frequency (MHz):(f1) 250.136 Original Points Count:(f1) 8192 Actual Points Count:(f1) 16384 Acquisition Time (sec):(f1) 1.3599 Spectral Width (ppm):(f1) 24.083 Pulse Program:.Temperature:297Number of Scans:64Acq. Date:Fri Jul 03 02:33:00 AM
O
O
OH
O
O
OHN
O HN
O
NH
NN
O
O
O
O
1
2
3
1'2'
3'
1'2'
3'
1'' 2 ''
1''2 ''
1a
2a3a
4a5a1b1c18c
H3C(H2C)16H2C-O-H2C
ppm (t1)3.504.004.50
0
50
100
4.49
7
4.01
83.
998
3.97
0
3.88
93.
862
3.84
83.
844
3.72
03.
694
3.64
1
3.54
53.
523
3.43
53.
423
3.41
13.
397
3.34
7
326
6
4.26
3.73
1.17
1.67
2.19
2.00
6.18
2.04
Date:14 Jul 2009Document's Title:G1ND18
Spectrum Title:G1ND18 CD3OD 1H
Frequency (MHz):(f1) 250.136 Original Points Count:(f1) 8192 Actual Points Count:(f1) 16384 Acquisition Time (sec):(f1) 1.3599 Spectral Width (ppm):(f1) 24.083 Pulse Program:.Temperature:297Number of Scans:64Acq. Date:Fri Jul 03 02:33:00 AM
O
O
OH
O
O
OHN
O HN
O
NH
NN
O
O
O
O
1
2
3
1'2'
3'
1'2'
3'
1'' 2 ''
1''2 ''
1a
2a3a
4a5a1b1c18c
H3C(H2C)16H2C-O-H2C
solvent peakmethanol-d4
O
O
OH
O
O
OHN
O HN
O
NH
NN
O
O
O
O
1
2
3
1'2'
3'
1'2'
3'
1'' 2''
1''2''
1a
2a3a
4a5a1b1c18c
H3C(H2C)16H2C-O-H2C
solvent peakmethanol-d4
O
O
OH
O
O
OHN
O HN
O
NH
NN
O
O
O
O
1
2
3
1'2'
3'
1'2'
3'
1'' 2''
1''2''
1a
2a3a
4a5a1b1c18c
H3C(H2C)16H2C-O-H2C
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2009
HRMS (ESI) of compound 17
1H NMR spectrum (Bruker DRX-400, 400 MHz, methanol-d4) of compound 18
O
O
OH
O
O
OHN
O HN
O
NH
NN
O
O
O
O
1
2
3
1'2'
3'
1'2'
3'
1'' 2''
1''2''
1a
2a3a
4a5a1b1c18c
H3C(H2C)16H2C-O-H2C
O
O
OH
O
O
OHN
O HN
O
NH
NN
O
O
O
O
1
2
3
1'2'
3'
1'2'
3'
1'' 2''
1''2''
1a
2a3a
4a5a1b1c18c
H3C(H2C)16H2C-O-H2C
solvent peakmethanol-d4
solvent peakmethanol-d4
CF3COO-O
O
OH
O
OH
OHN
O
NN
NH3+
1"2"3'
2 '1 '
1
2
3
1''' 2 '''
3 '''
1a
2a
3a
4a 5a1b1c18cH3C(H2C)16H2C-O-H2C
solvent peakmethanol-d4
solvent peakmethanol-d4
CF3COO-O
O
OH
O
OH
OHN
O
NN
NH3+
1"2"3'
2 '1 '
1
2
3
1''' 2 '''
3 '''
1a
2a
3a
4a 5a1b1c18cH3C(H2C)16H2C-O-H2C
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2009
1H NMR spectrum (Bruker DRX-400, 400 MHz, methanol-d4) of compound 18
(expansion from δ 3.28 to 4.56)
13C NMR spectrum (Bruker DRX-400, 100.5 MHz, methanol-d4) of compound 18
solvent peakmethanol-d4
CF3COO-O
O
OH
O
OH
OHN
O
NN
NH3+
1"2"3'
2'1'
1
2
3
1''' 2'''
3'''
1a
2a
3a
4a 5a1b1c18cH3C(H2C)16H2C-O-H2C
solvent peakmethanol-d4
CF3COO-O
O
OH
O
OH
OHN
O
NN
NH3+
1"2"3'
2'1'
1
2
3
1''' 2'''
3'''
1a
2a
3a
4a 5a1b1c18cH3C(H2C)16H2C-O-H2C
solvent peakmethanol-d4
TFA
CF3COO-O
O
OH
O
OH
OHN
O
NN
NH3+
1"2"3'
2'1'
1
2
3
1''' 2'''
3'''
1a
2a
3a
4a 5a1b1c18cH3C(H2C)16H2C-O-H2C
solvent peakmethanol-d4
TFA
CF3COO-O
O
OH
O
OH
OHN
O
NN
NH3+
1"2"3'
2'1'
1
2
3
1''' 2'''
3'''
1a
2a
3a
4a 5a1b1c18cH3C(H2C)16H2C-O-H2C
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2009
13C NMR spectrum (Bruker DRX-400, 100.5 MHz, methanol-d4) of compound 18
(expansion from δ 61.017 to 72.386)
HRMS (ESI) of compound 18
CF3COO -O
O
OH
O
O H
O HN
O
NN
NH3+
1"2"3'
2 '1 '
1
2
3
1''' 2 '''
3 '''
1a
2a
3a
4a 5a1b1c18cH 3C(H 2C)16H2C-O -H 2C
CF3COO -O
O
OH
O
O H
O HN
O
NN
NH3+
1"2"3'
2 '1 '
1
2
3
1''' 2 '''
3 '''
1a
2a
3a
4a 5a1b1c18cH 3C(H 2C)16H2C-O -H 2C
CF3COO-O
O
OH
O
OH
OHN
O
NN
NH3+
1"2"3'
2'1'
1
2
3
1''' 2'''
3'''
1a
2a
3a
4a 5a1b1c18cH3C(H2C)16H2C-O-H2C
CF3COO-O
O
OH
O
OH
OHN
O
NN
NH3+
1"2"3'
2'1'
1
2
3
1''' 2'''
3'''
1a
2a
3a
4a 5a1b1c18cH3C(H2C)16H2C-O-H2C
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2009
1H NMR spectrum (Bruker DRX-400, 400 MHz, methanol-d4) of compound 19
13C NMR spectrum (Bruker DRX-400, 100.5 MHz, methanol-d4) of compound 19
solvent peakmethanol-d4
solvent peakmethanol-d4
2C F 3C O O -O
O
O H
O
O
O HN
ON H 3
+
O
N H 3+
NN1
2
3
1'2 '
3 '
1 '2 '
3 '
1 '' 2 ''
1 ''2 ''
1a
2a3a
4a5a1b1c1 8c
H 3C (H 2C )16H 2C -O -H 2C
solvent peakmethanol-d4
solvent peakmethanol-d4
2C F 3C O O -O
O
O H
O
O
O HN
ON H 3
+
O
N H 3+
NN1
2
3
1'2 '
3 '
1 '2 '
3 '
1 '' 2 ''
1 ''2 ''
1a
2a3a
4a5a1b1c1 8c
H 3C (H 2C )16H 2C -O -H 2C
solvent peakmethanol-d4
2C F 3C O O -O
O
O H
O
O
O HN
ON H 3
+
O
N H 3+
NN1
2
3
1 '2 '
3 '
1 '2 '
3 '
1 '' 2 ''
1 ''2 ''
1a
2 a3 a
4 a5 a1b1 c1 8c
H 3C (H 2C )16H 2C -O -H 2C
solvent peakmethanol-d4
2C F 3C O O -O
O
O H
O
O
O HN
ON H 3
+
O
N H 3+
NN1
2
3
1 '2 '
3 '
1 '2 '
3 '
1 '' 2 ''
1 ''2 ''
1a
2 a3 a
4 a5 a1b1 c1 8c
H 3C (H 2C )16H 2C -O -H 2C
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2009
HRMS (ESI) of compound 19
1H NMR spectrum (Bruker DRX-400, 400 MHz, methanol-d4) of compound 25
HO
O
ONH
O
OO
O 1 2
3
1'2'
1''1'''
1''''
2''''3''''
5'''' 6''''
4''''
solvent peakmethanol-d4
solvent peakmethanol-d4
HO
O
ONH
O
OO
O 1 2
3
1'2'
1''1'''
1''''
2''''3''''
5'''' 6''''
4''''
HO
O
ONH
O
OO
O 1 2
3
1'2'
1''1'''
1''''
2''''3''''
5'''' 6''''
4''''
solvent peakmethanol-d4
solvent peakmethanol-d4
2CF3COO-O
O
OH
O
O
OHN
ONH3
+
O
NH3+
NN1
2
3
1'2'
3'
1'2'
3'
1'' 2''
1''2''
1a
2a3a
4a5a1b1c18c
H3C(H2C)16H2C-O-H2C2CF3COO-
O
O
OH
O
O
OHN
ONH3
+
O
NH3+
NN1
2
3
1'2'
3'
1'2'
3'
1'' 2''
1''2''
1a
2a3a
4a5a1b1c18c
H3C(H2C)16H2C-O-H2C
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2009
13C NMR spectrum (Bruker DRX-400, 100.5 MHz, methanol-d4) of compound 25
1H NMR spectrum (Bruker DRX-400, 400 MHz, methanol-d4) of compound 29
HO
O
ONH
O
OO
O 1 2
3
1'2'
1''1'''
1''''
2''''3''''
5'''' 6''''
4''''
solvent peakmethanol-d4
HO
O
ONH
O
OO
O 1 2
3
1'2'
1''1'''
1''''
2''''3''''
5'''' 6''''
4''''
HO
O
ONH
O
OO
O 1 2
3
1'2'
1''1'''
1''''
2''''3''''
5'''' 6''''
4''''
solvent peakmethanol-d4
HO
O2N O
ONH
O
O
OH
12
1'
2'
3'1''
solvent peakmethanol-d4
solvent peakmethanol-d4
HO
O2N O
ONH
O
O
OH
12
1'
2'
3'1''
HO
O2N O
ONH
O
O
OH
12
1'
2'
3'1''
solvent peakmethanol-d4
solvent peakmethanol-d4
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2009
13C NMR spectrum (Bruker DRX-400, 100.5 MHz, methanol-d4) of compound 29
Supplementary Material (ESI) for Organic & Biomolecular Chemistry HRMS (ESI) of compound 29
HO
O2N O
ONH
O
O
OH
12
1'
2'
3'1''
solvent peakmethanol-d4
HO
O2N O
ONH
O
O
OH
12
1'
2'
3'1''
HO
O2N O
ONH
O
O
OH
12
1'
2'
3'1''
solvent peakmethanol-d4
HO
O2N O
ONH
O
O
OH
12
1'
2'
3'1''
HO
O2N O
ONH
O
O
OH
12
1'
2'
3'1''