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Supporting Information
Merging Visible-Light Photoredox and Lewis Acid Catalysis
for the Functionalization and Arylation of Glycine Derivatives
and Peptides
Shaoqun Zhu and Magnus Rueping* Institute of Organic Chemistry, RWTH Aachen University
Landoltweg 1, 52074 Aachen, Germany
General: Unless otherwise noted, all commercially available compounds were used as
provided without further purification. Solvents used in reactions were p.A. grade and dried
only if indicated. Solvents for chromatography were technical grade and distilled prior to use.
Analytical thin-layer chromatography (TLC) was performed on Merck silica gel aluminium
plates with F-254 indicator, visualised by irradiation with UV light. Column chromatography
was performed using silica gel Merck 60 (particle size 0.063 – 0.2 mm). Solvent mixtures are
understood as volume/volume.
1H-NMR and 13C-NMR were recorded on a Varian VNMR 400 and VNMR 600 spectrometer
in CDCl3. Data are reported in the following order: chemical shift (δ) in ppm; multiplicities
are indicated br (broadened singlet), s (singlet), d (doublet), t (triplet), q (quartet), quint
(quintet), m (multiplet); coupling constants (J) are in Hertz (Hz). Mass spectra (MS-EI, 70
eV) were conducted on a Finnigan SSQ 7000 spectrometer. IR spectra were recorded on a
Perkin Elmer Spectrum 100 FT-IR spectrometer and are reported in terms of frequency of
absorption (cm-1). Glycine ester and glycine derived dipeptides were prepared according to
the literature reports.1-3
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
2
General Procedure for the Photoredox Catalyzed Functionalization of Glycine Esters.
In a vial [Ir(ppy)2bpy]PF6 (0.002 mmol), glycine ester 1 (0.2 mmol), Zn(OAc)2 (0.02 mmol)
and indole 2 (0.3 mmol) were dissolved in the solvent indicated and the reaction mixture was
stirred for the time indicated under irradiation with the light source as indicated (fluorescent
bulb Osram Dulux S 11W, distance app. 5cm). The reaction was monitored via TLC
(hexanes: ethyl acetate). Upon consumption of the starting material, the crude mixture was
purified by column chromatography (hexanes: ethyl acetate) to yield the corresponding
products 3a-y.
General Procedure for the Photoredox Catalyzed Functionalization of Dipeptides.
In a vial [Ir(ppy)2bpy]PF6 (0.002 mmol), dipeptide 5 (0.2 mmol), Zn(OAc)2 (0.2 mmol) and
indole 2 (0.3 mmol) were dissolved in MeCN (2 mL) and the reaction mixture was stirred for
the time indicated under irradiation with the light source as indicated (fluorescent bulb Osram
Dulux S 11W, distance app. 5cm). The reaction was monitored via TLC (hexanes: ethyl
acetate). Upon consumption of the starting material the crude mixture was purified by column
chromatography (hexanes: ethyl acetate) to yield the corresponding products 6a-j.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
3
Table 1. Slovent, oxidant and additive screening for the photoredox catalyzed
functionalization of glycine esters.[a]
Ir(ppy)2(bpy)PF6 (1mol%)
HN
OEt
O
11 W fluorescent bulb
HN
+NH Zn(OAc)2 10 mol%, MeCN
HN
OEt
O
1a 2a 3a
Entry Solvent Oxidant Additive Yield(%)[b]
1 MeCN Air none 72% 2 MeCN BrCCl3 none 50%
3 MeCN Oxygen none low conv.
4 MeCN Air NaOAc low conv.
5 MeCN Air N,N-diisopropylethylamine low conv.
6 MeCN Air 4Å MS -
7 Toluene Air none low conv.
8 THF Air none low conv.
9 DMSO Air none -
10 DMF Air none < 10%
11 iPrOH Air none -
12 DCM Air none < 10%
13 NMP Air none -
14 MeCN Air Water (0.5 ml) -
15 EtCN Air none 62% [a] Reaction conditions: 1a (0.2 mmol), 2a (0.3 mmol), catalyst (1 mol%), 11W fluorescent bulb, MeCN (2.0 mL), 48 h. [b] Yield of the isolated product.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4
Table 2. Lewis acid screening for the photoredox catalyzed functionalization of dipeptides.[a]
Ir(ppy)2(bpy)PF6 (1mol%)HN
NH
O
11 W fluorescent bulb
HN
+NH Lewis acid X mol%, MeCN
OEt
O
HN
NH
O
OEt
O
5a 2a6a
Entry Lewis acid X Yield(%)[b]
1 CuBr 10% Trace product
2 CuCl 10% -
3 CuI 10% < 10%
4 Cu(OAc)2 10% Trace product
5 Cu(OTf)2 10% -
6 Zn(OTf)2 10% -
7 Zn(OAc)2 10% 40% conversion
8 Zn(OAc)2 100% 60% [a] Reaction conditions: 5a (0.2 mmol), 2a (0.3 mmol), catalyst (1 mol%), 11W fluorescent bulb, and MeCN (2.0 mL), 48h. [b] Yield of the isolated product.
Characterization of the products.
Ethyl 2-(1H-indol-2-yl)-2-(1H-indol-3-yl)acetate:[4] 1H-NMR (600 MHz, CDCl3): δ = 8.01
(br, 2H), 7.65 (d, J = 7.8 Hz, 2H), 7.34 (d, J = 8.4 Hz, 1H), 7.20 – 7.10
(m, 6H), 5.51 (s, 1H), 4.24 (q, J = 7.2 Hz 2H), 1.27 (t, J = 7.2 Hz, 3H); 13C-NMR (150.8 MHz, CDCl3): δ = 173.4, 136.3, 126.7, 123.3, 122.1,
119.5, 119.3, 113.7, 111.2, 61.1, 40.7, 14.2; IR (neat): ν = 3411, 3011,
1721, 1457, 1216, 755; MS-EI: m/z(%): 245.3 (100%, M+ – CO2Et),
318.3 (M+, 23%), 319.3 (M++1, 5%).
Ethyl 2-(1H-indol-3-yl)-2-(phenylamino)acetate: 24h, 74% yield, 1H-NMR (400 MHz,
CDCl3): δ = 8.12 (br, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.35 (d, J = 8.0
Hz, 1H), 7.24 – 7.20 (m, 2H), 7.18 – 7.12 (m, 3H), 6.73 – 6.69 (m,
1H), 6.64 – 6.62 (m, 2H), 5.38 (s, 1H), 4.75 (br, 1H), 4.30 – 4.04
(m, 2H), 1.21 (t, J = 7.2 Hz, 3H); 13C-NMR (100.6 MHz, CDCl3): δ
= 172.5, 146.5, 136.5, 129.2, 125.8, 123.0, 122.5, 120.0, 119.6, 118.0, 113.4, 112.7, 111.3,
61.6, 54.2, 14.1; IR (neat): ν = 3410, 3010, 2980, 1728, 1603, 1504, 1313, 1218, 1187, 1019,
693, 666, 532; MS-EI: m/z(%): 221.3 (100%, M+ – CO2Et), 294.3 (M+, 14%), 295.3 (M++1,
3%).
NHO
O
HN
HN
NHO
O
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Ethyl 2-(1H-indol-3-yl)-2-(p-tolylamino)acetate: 30h, 72% yield, 1H-NMR (600 MHz,
CDCl3): δ = 8.17 (br, 1H), 7.85 (d, J = 7.8 Hz, 1H), 7.35 (d, J =
8.4 Hz, 1H), 7.26 – 7.16 (m, 3H), 6.98 (m, 2H), 6.59 (m, 2H), 5.38
(s, 1H), 4.63 (br, 1H), 4.30 – 4.11 (m, 2H), 2.23 (s, 3H), 1.23 (t,
J = 7.2 Hz, 3H); 13C-NMR (150.8 MHz, CDCl3): δ = 172.7, 144.3,
136.5, 129.7, 127.3, 125.8, 123.0, 122.5, 120.0, 119.6, 113.6, 112.7, 111.4, 61.5, 54.6, 14.1;
IR (neat): ν = 3407, 3009, 2921, 1729, 1617, 1518, 1307, 1216, 1191, 1018, 812, 754, 666,
506; MS-EI: m/z(%): 235.3 (100%, M+ – CO2Et), 308.3 (M+, 24%), 309.3 (M++1, 5%).
Isopropyl 2-(1H-indol-3-yl)-2-(p-tolylamino)acetate: 36h, 73% yield, 1H-NMR (400 MHz,
CDCl3): δ = 8.16 (br, 1H), 7.84 (d, J = 8.0 Hz, 1H), 7.34 (d, J =
8.0 Hz, 1H), 7.24 – 7.13 (m, 3H), 6.97 – 6.95 (m, 2H), 6.59 – 6.55
(m, 2H), 5.34 (s, 1H), 5.08 – 5.02 (m, 1H), 3.98 (br, 1H), 2.22 (s,
3H), 1.28 (d, J = 6.4 Hz, 3H), 1.08 (t, J = 6.0 Hz, 3H); 13C-NMR
(100.6 MHz, CDCl3): δ = 172.2, 144.3, 136.5, 129.7, 127.2, 125.8,
122.9, 122.4, 119.8, 119.7, 113.5, 112.8, 111.3, 69.2, 54.7, 21.8 (d, J = 32.8 Hz, 1C), 20.4; IR
(neat): ν = 3407, 2982, 2930, 1725, 1616, 1519, 1305, 1216, 1103, 949, 813, 754, 667, 506;
MS-EI: m/z(%): 235.3 (100%, M+ – CO2iPr), 322.3 (M+, 18%), 323.4 (M++1, 5%).
Methyl 2-(1H-indol-3-yl)-2-(p-tolylamino)acetate: 36h, 71% yield, 1H-NMR (400 MHz,
CDCl3): δ = 8.15 (br, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.36 (d, J = 8.0
Hz, 1H), 7.24 – 7.14 (m, 3H), 6.97 – 6.95 (m, 2H), 6.58 – 6.55 (m,
2H), 5.38 (s, 1H), 4.60 (br, 1H), 3.72 (s, 3H), 2.21 (s, 3H); 13C-NMR
(100.6 MHz, CDCl3): δ = 173.2, 144.2, 136.4, 129.7, 127.4, 125.8,
123.0, 122.5, 120.1, 119.4, 113.5, 112.6, 111.4, 54.4, 52.5, 20.4; IR (neat): ν = 3409, 3015,
2954, 1736, 1616, 1519, 1308, 1216, 1100, 985, 812, 757, 667, 506; MS-EI: m/z(%): 235.3
(100%, M+ – CO2Me), 294.4 (M+, 38%), 295.3 (M++1, 7%).
Tert-butyl 2-(1H-indol-3-yl)-2-(p-tolylamino)acetate: 36h, 45% yield, 1H-NMR (400 MHz,
CDCl3): δ = 8.10 (br, 1H), 7.84 (d, J = 7.6 Hz, 1H), 7.37 (d, J = 8.0
Hz, 1H), 7.28 – 7.14 (m, 3H), 6.96 – 6.94 (m, 2H), 6.57 – 6.54 (m,
2H), 5.27 (s, 1H), 4.58 (br, 1H), 2.22 (s, 3H), 1.40 (s, 9H); 13C-
NMR (100.6 MHz, CDCl3): δ = 171.8, 144.4, 136.5, 129.6, 127.0,
NHO
O
HN
O
O
NH
HN
O
O
NH
HN
O
O
NH
HN
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
6
126.0, 122.8, 122.3, 119.8, 119.7, 113.5, 113.3, 111.2, 82.0, 55.1, 27.9, 20.4; IR (neat): ν =
3408, 3008, 2979, 1724, 1616, 1519, 1154, 812, 757, 667, 506; MS-EI: m/z(%): 235.4 (100%,
M+ – CO2tBu), 336.4 (M+, 38%), 337.4 (M++1, 19%).
Benzyl 2-(1H-indol-3-yl)-2-(p-tolylamino)acetate: 36h, 83% yield, 1H-NMR (400 MHz,
CDCl3): δ = 8.10 (br, 1H), 7.84 (d, J = 7.6 Hz, 1H), 7.37 (d, J =
8.4 Hz, 1H), 7.28 – 7.11 (m, 9H), 6.96 – 6.94 (m, 2H), 6.58 –
6.55 (m, 2H), 5.44 (s, 1H), 5.25 (d, J = 12.0 Hz, 1H), 5.10 (d, J =
12.0 Hz, 1H), 4.60 (br, 1H), 2.22 (s, 3H); 13C-NMR (100.6 MHz,
CDCl3): δ = 172.6, 144.2, 136.4, 135.4, 129.7, 128.4, 128.2,128.1, 127.4, 125.8, 123.0, 122.5,
120.0, 119.6, 113.6, 112.5, 111.3, 67.1, 54.6, 20.4; IR (neat): ν = 3471, 3419, 3352, 3018,
1733, 1519, 1216, 809, 757, 668, 507; MS-EI: m/z(%): 235.3 (100%, M+ – CO2Bn), 370.3
(M+, 30%), 371.3 (M++1, 19%).
Ethyl 2-(1H-indol-3-yl)-2-((4-methoxyphenyl)amino)acetate: 36h, 76% yield, 1H-NMR
(400 MHz, CDCl3): δ = 8.15 (br, 1H), 7.83 (d, J = 7.6 Hz, 1H),
7.36 (d, J = 8.4 Hz, 1H), 7.24 – 7.13 (m, 3H), 6.76 – 6.72 (m,
2H), 6.63 – 6.59 (m, 2H), 5.32 (s, 1H), 4.47 (br, 1H), 4.28-
4.08 (m, 2H), 3.71 (s, 3H), 1.20 (t, J = 7.2 Hz, 1H); 13C-NMR
(100.6 MHz, CDCl3): δ = 172.7, 152.5, 140.8, 136.4, 125.8, 122.9, 122.5, 120.0, 119.6, 114.8
(2C), 112.9, 111.3, 61.5, 55.7, 55.2, 14.1; IR (neat): ν = 3407, 3003, 2937, 2907, 1730, 1513,
1459, 1302, 1239, 1191, 1099, 1031, 823, 757, 668, 507; MS-EI: m/z(%): 251.3 (100%, M+ –
CO2Et), 324.3 (M+, 34%), 325.3 (M++1, 8%).
Ethyl 2-((4-chlorophenyl)amino)-2-(1H-indol-3-yl)acetate: 48h, 76% yield, 1H-NMR (600
MHz, CDCl3): δ = 8.17 (br, 1H), 7.81 (d, J = 7.8 Hz, 1H), 7.37
(d, J = 8.4 Hz, 1H), 7.25 – 7.16 (m, 3H), 7.09 – 7.06 (m, 2H),
6.56 – 6.53 (m, 2H), 5.34 (s, 1H), 4.80 (br, 1H), 4.29-4.10 (m,
2H), 1.21 (t, J = 7.2 Hz, 1H); 13C-NMR (150.8 MHz, CDCl3): δ
= 172.2, 145.0, 136.5, 129.0, 125.7, 123.0, 122.6, 121.4, 120.1, 119.5, 114.5, 112.2, 111.4,
61.7, 54.3, 14.1; IR (neat): ν = 3407, 3003, 2937, 2907, 1730, 1513, 1459, 1302, 1239, 1191,
1099, 1031, 823, 757, 668, 507; MS-EI: m/z(%): 255.3 (100%, M+ – CO2Et), 328.3 (M+,
23%), 329.3 (M++1, 8%).
O
O
NH
Ph
HN
NHO
O
MeO
HN
NHO
O
Cl
HN
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7
Benzyl 2-(1-methyl-1H-indol-3-yl)-2-(p-tolylamino)acetate: 36h, 68% yield, 1H-NMR (400
MHz, CDCl3): δ = 7.77 (d, J = 8.0 Hz, 1H), 7.34 – 7.10 (m, 8H), 7.01
(s, 1H), 6.94 (d, J = 8.4 Hz, 1H), 6.57 – 6.53 (m, 2H), 5.41 (d, J =
6.0 Hz, 1H), 5.25 (d, J = 12.0 Hz, 1H), 5.09 (d, J = 12.0 Hz, 1H),
4.56 (d, J = 6.0 Hz, 1H), 3.70 (s, 3H), 2.21 (s, 3H); 13C-NMR (100.6
MHz, CDCl3): δ = 172.7, 144.3, 137.2, 135.5, 129.7, 128.4, 128.2
(2C), 127.6, 127.3, 126.3, 122.1, 119.7, 119.6, 113.5, 110.8, 109.4, 67.1, 54.5, 32.8, 20.4; IR
(neat): ν = 3404, 3036, 2923, 1735, 1613, 1519, 1466, 1380, 1317, 1163, 1020, 963, 812, 744,
608, 507; MS-EI: m/z(%): 249.3 (100%, M+ – CO2Bn), 384.4 (M+, 16%), 385.4 (M++1, 4%).
Ethyl 2-(1-methyl-1H-indol-3-yl)-2-(p-tolylamino)acetate: 48h, 60% yield, 1H-NMR (600
MHz, CDCl3): δ = 7.83 (d, J = 7.8 Hz, 1H), 7.32 – 6.57 (m, 8H), 5.35
(s, 1H), 4.60 (s, 1H), 4.29 – 4.10 (m, 2H), 3.74 (s, 3H), 2.22 (s, 3H),
1.23 (t, J = 6.8 Hz, 3H); 13C-NMR (150.8 MHz, CDCl3): δ = 172.8,
144.3, 137.3, 129.7, 127.5, 127.2, 126.3, 122.0, 119.7, 119.5, 113.5,
111.1, 109.4, 61.4, 54.5, 32.8, 20.4, 14.1; IR (neat): ν = 3404, 3036,
2923, 1735, 1613, 1519, 1466, 1380, 1317, 1163, 1020, 963, 812, 744, 608, 507; MS-EI:
m/z(%): 249.4 (100%, M+ – CO2Et), 322.4 (M+, 16%), 323.4 (M++1, 4%).
Ethyl 2-(1-(tert-butyldimethylsilyl)-1H-indol-3-yl)-2-(p-tolylamino)acetate: 36h, 42%
yield, 1H-NMR (400 MHz, CDCl3): δ = 7.80 – 7.77 (m, 1H), 7.50
– 6.56 (m, 8H), 5.34 (s, 1H), 4.51 (s, 1H), 4.28 – 4.11 (m, 2H),
2.21 (s, 3H), 1.22 (t, J = 7.2 Hz, 3H), 0.88 (s, 9H), 0.58 (d, J = 3.2
Hz, 6H); 13C-NMR (100.6 MHz, CDCl3): δ = 172.8, 144.5, 141.6,
129.7 (2C), 129.2, 127.3, 121.9, 120.0, 119.4, 114.5, 114.1, 113.6,
61.3, 54.7, 26.2, 20.4, 19.4, 14.2, –4.0; IR (neat): ν = 3401, 2920, 2854, 1726, 1622, 1579,
1544, 1452, 1383, 1064, 794, 741, 592; MS-EI: m/z(%): 349.4 (100%, M+ – CO2Et), 422.5
(M+, 18%), 423.5 (M++1, 7%).
Isopropyl 2-(1-methyl-1H-indol-3-yl)-2-(p-tolylamino)acetate: 36h, 55% yield, 1H-NMR
(400 MHz, CDCl3): δ = 7.82 – 7.80 (m, 1H), 7.31 – 6.54 (m, 8H),
5.30 (s, 1H), 5.09 – 4.98 (m, 1H), 4.58 (s, 1H), 3.73 (s, 3H), 2.21
(s, 3H), 1.28 (d, J = 6.0 Hz, 3H), 1.09 (d, J = 6.0 Hz, 3H); 13C-
NMR (100.6 MHz, CDCl3): δ = 172.3, 144.4, 137.3, 129.7, 127.5,
127.1, 126.4, 121.9, 119.8, 119.4, 113.5, 111.2, 109.4, 69.1, 54.7,
O
O
NH
N
Ph
O
O
NH
N
NHO
O
NTBS
NH O
O
N
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8
32.9, 21.8 (d, J = 32.2 Hz, 1C), 20.4; IR (neat): ν = 3404, 2922, 2422, 1728, 1615, 1524,
1462, 1381, 1103, 815, 746, 612; MS-EI: m/z(%): 249.4 (100%, M+ – CO2iPr), 336.4 (M+,
19%), 337.4 (M++1, 4%).
Methyl 2-(5-fluoro-1H-indol-3-yl)-2-(p-tolylamino)acetate: 72h, 56% yield, 1H-NMR (400
MHz, CDCl3): δ = 8.18 (br, 1H), 7.47 – 7.44 (m, 1H), 7.26 – 6.53
(m, 7H), 5.30 (s, 1H), 4.62 (br, 1H), 3.70 (s, 3H), 2.21 (s, 3H); 13C-
NMR (100.6 MHz, CDCl3): δ = 173.0, 159.1 (d, J = 235.5 Hz, 1C),
144.0, 132.9, 129.8, 127.5, 126.2 (d, J = 10.0 Hz, 1C), 124.7,
113.6, 112.8 (d, J = 4.6 Hz, 1C), 112.1 (d, J = 9.6 Hz, 1C), 111.2
(d, J = 26.0 Hz, 1C), 104.6 (d, J = 24.0 Hz, 1C), 54.3, 52.6, 20.4; IR (neat): ν = 3412, 2920,
2856, 1733, 1623, 1582, 1452, 1384, 1066, 804, 723, 617; MS-EI: m/z(%): 253.3 (100%, M+
– CO2Me), 312.3 (M+, 52%), 313.3 (M++1, 12%).
Methyl 2-(6-methyl-1H-indol-3-yl)-2-(p-tolylamino)acetate: 48h, 82% yield, 1H-NMR (400
MHz, CDCl3): δ = 8.02 (br, 1H), 7.70 (d, J = 8.0 Hz, 1H), 7.16 –
6.55 (m, 7H), 5.36 (s, 1H), 4.61 (br, 1H), 3.73 (s, 3H), 2.47 (s, 3H),
2.22 (s, 3H); 13C-NMR (100.6 MHz, CDCl3): δ = 173.2, 144.2,
136.9, 132.5, 129.7, 127.3, 123.6, 122.4, 121.9, 119.1, 113.5, 112.5,
111.3, 54.5, 52.5, 21.7, 20.4; IR (neat): ν = 3425, 2920, 2855, 1731,
1629, 1579, 1546, 1384, 1065, 879, 670; MS-EI: m/z(%): 249.3 (100%, M+ – CO2Me), 308.3
(M+, 55%), 309.3 (M++1, 12%).
Methyl 2-(5-cyano-1H-indol-3-yl)-2-(p-tolylamino)acetate: 36h, 75% yield, 1H-NMR (400
MHz, CDCl3): δ = 8.72 (br, 1H), 8.20 – 8.19 (m, 1H), 7.45 –
6.53 (m, 7H), 5.36 (s, 1H), 3.75 (s, 3H), 3.70 (br, 1H), 2.22 (s,
3H); 13C-NMR (100.6 MHz, CDCl3): δ = 172.5, 143.7, 138.2,
129.8 (2), 127.8, 125.6, 125.3 (2), 120.5, 113.7, 113.6, 112.4,
103.2, 54.2, 52.8, 20.4; IR (neat): ν = 3424, 2920, 2854, 2222, 1734, 1625, 1579, 1543, 1448,
1384, 1064, 879, 643; MS-EI: m/z(%): 260.4 (100%, M+ – CO2Me), 319.4 (M+, 55%), 320.4
(M++1, 12%).
O
O
NH
HN
F
O
O
NH
HN
NHO
O
HNCN
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9
Methyl 3-(2-methoxy-2-oxo-1-(p-tolylamino)ethyl)-1H-indole-5-carboxylate: 36h, 67%
yield, 1H-NMR (400 MHz, CDCl3): δ = 8.59 (br, 1H), 8.56
(d, J = 8.0 Hz, 1H), 7.92 – 6.54 (m, 7H), 5.41 (s, 1H), 3.93
(s, 3H), 3.72 (s, 3H), 3.62 (br, 1H), 2.20 (s, 3H); 13C-NMR
(100.6 MHz, CDCl3): δ = 173.0, 168.1, 144.0, 139.0, 129.8,
127.6, 125.4, 124.4, 123.9, 122.3, 122.2, 114.2, 113.6, 111.2, 54.1, 52.6, 51.9, 20.4; IR (neat):
ν = 3364, 2920, 2854, 2575, 1729, 1687, 1624, 1582, 1437, 1384, 1065, 751, 621; MS-EI:
m/z(%): 293.4 (100%, M+ – CO2Me), 352.3 (M+, 25%), 353.3 (M++1, 5%).
Methyl 2-(2-phenyl-1H-indol-3-yl)-2-(p-tolylamino)acetate: 36h, 65% yield, 1H-NMR (400
MHz, CDCl3): δ = 8.24 (br, 1H), 7.94 – 7.91 (m, 1H), 7.71 – 6.38
(m, 12H), 5.47 (s, 1H), 4.73 (br, 1H), 3.75 (s, 3H), 2.19 (s, 3H); 13C-
NMR (100.6 MHz, CDCl3): δ = 173.2, 144.0, 137.3, 135.8, 132.0,
129.6, 129.0, 128.8, 128.6, 127.0, 126.6, 122.6, 120.4, 120.0, 113.3,
111.1, 108.5, 53.9, 52.5, 20.3; IR (neat): ν = 3411, 2920, 2854,
2025, 1734, 1449, 1384, 1062, 878, 742; MS-EI: m/z(%): 311.3 (100%, M+ – CO2Me), 370.4
(M+, 22%), 371.4 (M++1, 6%).
Methyl 2-(7-methyl-1H-indol-3-yl)-2-(p-tolylamino)acetate: 36h, 86% yield, 1H-NMR (400
MHz, CDCl3): δ = 8.05 (br, 1H), 7.66 – 7.64 (m, 1H), 7.23 – 6.54 (m,
7H), 5.37 (s, 1H), 4.61 (br, 1H), 3.72 (s, 3H), 2.46 (s, 3H), 2.20 (s,
3H); 13C-NMR (100.6 MHz, CDCl3): δ = 173.2, 144.2, 136.0, 129.7,
127.3, 125.3, 123.1, 122.7, 120.5, 120.3, 117.1, 113.5, 113.2, 54.5,
52.5, 20.4, 16.5; IR (neat): ν = 3411, 3014, 2922, 2861, 1735, 1616,
1519, 1439, 1311, 1212, 1011, 811, 755; MS-EI: m/z(%): 249.3 (100%, M+ – CO2Me), 308.3
(M+, 54%), 309.4 (M++1, 11%).
Methyl 2-(5-iodo-1H-indol-3-yl)-2-(p-tolylamino)acetate: 36h, 52% yield, 1H-NMR (400
MHz, CDCl3): δ = 8.26 (br, 1H), 8.13(d, J = 8.0 Hz, 1H), 7.46 –
6.53 (m, 7H), 5.30 (s, 1H), 4.56 (br, 1H), 3.73 (s, 3H), 2.21 (s, 3H),
2.20 (s, 3H); 13C-NMR (100.6 MHz, CDCl3): δ = 172.9, 143.9,
135.5, 130.9, 129.8, 128.3, 128.2, 127.6, 123.8, 119.8, 113.6, 113.3,
112.0, 83.7, 54.2, 52.6, 20.4; IR (neat): ν = 3402, 3014, 2923, 2865,
1733, 1614, 1519, 1448, 1309, 1217, 1004, 804, 757, 596, 504; MS-EI: m/z(%): 361.2 (100%,
M+ – CO2Me), 420.2 (M+, 44%), 421.2 (M++1, 8%).
NHO
O
HN O
O
NH O
O
HN
Ph
O
O
NH
HN
O
O
NH
HN
I
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10
Methyl 2-(5-bromo-1-methyl-1H-indol-3-yl)-2-(p-tolylamino)acetate: 36h, 68% yield, 1H-
NMR (400 MHz, CDCl3): δ = 7.94 (d, J = 6.0 Hz, 1H), 7.35 – 6.55
(m, 7H), 5.30 (s, 1H), 4.62 (br, 1H), 3.75 (s, 3H), 3.72 (s, 3H),
2.23 (s, 3H); 13C-NMR (100.6 MHz, CDCl3): δ = 172.9, 144.0,
135.9, 129.7, 128.7, 127.9, 127.5, 125.0, 122.1, 113.5, 113.1,
111.0, 110.8, 54.1, 52.6, 33.0, 20.4; IR (neat): ν = 3403, 3014,
2924, 1865, 1738, 1616, 1520, 1471, 1435, 1380, 1307, 864, 800, 757, 616, 507; MS-EI:
m/z(%): 327.2 (100%, M+ – CO2Me), 386.2 (M+, 39%), 387.2 (M++1, 11%).
Methyl 2-(5-bromo-1H-indol-3-yl)-2-(p-tolylamino)acetate: 36h, 54% yield, 1H-NMR (400
MHz, CDCl3): δ = 8.28 (br, 1H), 7.94 (m, 1H), 7.31 – 6.55 (m,
7H), 5.32 (s, 1H), 4.24 (br, 1H), 3.75 (s, 3H), 2.23 (s, 3H); 13C-
NMR (100.6 MHz, CDCl3): δ = 172.9, 144.0, 135.1, 129.8, 127.6,
127.5, 125.4, 124.2, 122.0, 113.6, 113.4, 112.8, 112.4, 54.2, 52.6,
20.4; IR (neat): ν = 3401, 3016, 2922, 2865, 1734, 1614, 1520, 1451, 1310, 1380, 1217, 1107,
882, 804, 757, 602, 505; MS-EI: m/z(%): 313.2 (100%, M+ – CO2Me), 372.2 (M+, 42%),
373.2 (M++1, 9%).
Methyl 2-(1,2-dimethyl-1H-indol-3-yl)-2-(p-tolylamino)acetate: 36h, 50% yield, 1H-NMR
(400 MHz, CDCl3): δ = 7.90 (br, 1H), 7.78 – 6.52 (m, 8H), 5.29 (s,
1H), 4.57 (br, 1H), 3.70 (s, 3H), 2.48 (s, 3H), 2.21 (s, 3H); 13C-NMR
(100.6 MHz, CDCl3): δ = 172.9, 144.0, 135.1, 129.8, 127.6, 127.5,
125.4, 124.2, 122.0, 113.6, 113.4, 112.8, 112.4, 54.2, 52.4, 20.4, 12.1;
IR (neat): ν = 3401, 3016, 2922, 2865, 1734, 1614, 1520, 1451, 1310, 1380, 1217, 1107, 882,
804, 757, 602, 505; MS-EI: m/z(%): 249.2 (100%, M+ – CO2Me), 308.2 (M+, 42%), 309.2
(M++1, 9%).
Methyl 2-(5-methoxy-1H-indol-3-yl)-2-(p-tolylamino)acetate: 36h, 69% yield, 1H-NMR
(400 MHz, CDCl3): δ = 8.05 (br, 1H), 7.27 – 6.56 (m, 8H), 5.34
(s, 1H), 4.53 (br, 1H), 3.87 (s, 3H), 3.75 (s, 3H), 2.22 (s, 3H); 13C-NMR (100.6 MHz, CDCl3): δ = 173.2, 154.4, 144.3, 131.5,
129.7, 127.4, 126.2, 123.7, 113.5, 112.9, 112.4, 112.1, 101.1,
55.9, 54.4, 52.5, 20.4; IR (neat): ν = 3403, 3005, 2922, 2856,
1734, 1618, 1518, 1481, 1383, 1307, 1211, 1176, 1028, 925, 809, 755, 638, 505; MS-EI:
m/z(%): 265.3 (100%, M+ – CO2Me), 324.3 (M+, 57%), 325.3 (M++1, 11%).
O
O
NH
N
Br
O
O
NH
HN
Br
O
O
NH
HN
O
O
NH
HN
O
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11
Methyl 2-(5-methyl-1H-indol-3-yl)-2-(p-tolylamino)acetate: 36h, 70% yield, 1H-NMR (400
MHz, CDCl3): δ = 8.06 (br, 1H), 7.59 – 6.57 (m, 8H), 5.36 (s, 1H),
4.55 (br, 1H), 3.74 (s, 3H), 2.48 (s, 3H), 2.23 (s, 3H); 13C-NMR
(100.6 MHz, CDCl3): δ = 173.3, 144.3, 134.7, 129.7, 129.5, 127.3,
126.0, 124.2, 123.1, 118.9, 113.5, 112.1, 111.0, 54.4, 52.5, 21.5,
20.4; IR (neat): ν = 3350, 2970, 2922, 1736, 1614, 1517, 1461, 1378, 1306, 1232, 1119, 949,
814, 756, 615; MS-EI: m/z(%): 249.3 (100%, M+ – CO2Me), 308.3 (M+, 60%), 309.3 (M++1,
13%).
Methyl 2-(p-tolylamino)-2-(2,4,6-trimethoxyphenyl)acetate: 36h, 71% yield, 1H-NMR
(400 MHz, CDCl3): δ = 6.94 – 6.92 (m, 2H), 6.66 – 6.64 (m, 2H), 6.12
(s, 2H), 5.67 (s, 1H), 4.77 (br, 1H), 3.84 (s, 6H), 3.78 (s, 3H), 3.67 (s,
3H), 2.20 (s, 3H); 13C-NMR (100.6 MHz, CDCl3): δ = 173.5, 160.9,
158.7, 145.0, 129.5, 126.9, 114.0, 108.5, 91.0, 55.9, 55.3, 52.3, 51.2,
20.4; IR (neat): ν = 3404, 3011, 2945, 2848, 1742, 1606, 1521, 1459,
1304, 1216, 1120, 813, 756, 665; MS-EI: m/z(%): 286.3 (100%, M+ –
CO2Me), 345.3 (M+, 11%), 346.3 (M++1, 3%).
Ethyl 2-(2-(1H-indol-3-yl)-2-(p-tolylamino)acetamido)acetate: 48h, 60% yield, 1H-NMR
(600 MHz, CDCl3): δ = 8.44 (br, 1H), 7.64 – 6.61 (m,
10H), 5.09 (s, 2H), 4.32– 4.28 (m, 1H), 4.20 – 4.16 (m,
1H), 3.90 – 3.86 (m, 1H), 2.27 (s, 3H), 1.25 (t, J = 7.2 Hz,
3H); 13C-NMR (150.8 MHz, CDCl3): δ = 172.7, 169.8,
144.7, 136.4, 129.9, 128.6, 125.7, 123.5, 122.6, 120.1,
118.8, 113.9, 113.2, 111.6, 61.5, 57.6, 41.2, 20.4, 14.1; IR (neat): ν = 3377, 3239, 2982, 2917,
2858, 1732, 1657, 1618, 1515, 1451, 1348, 1206, 1111, 810, 738, 671; MS-EI: m/z(%): 235.3
(100%, M+ – CONHCH2CO2Et), 365.3 (M+, 7%), 366.3 (M++1, 2%).
Ethyl 2-(2-(1-(tert-butyldimethylsilyl)-1H-indol-3-yl)-2-(p-tolylamino)acetamido)acetate:
48h, 68% yield, 1H-NMR (600 MHz, CDCl3): δ = 7.67 –
7.61 (m, 2H), 7.52 (d, J = 7.2 Hz, 1H), 7.40 (s, 1H), 7.20 –
6.63 (m, 6H), 5.08 (s, 1H), 4.35 – 4.29 (m, 1H), 4.29
(br,1H), 4.21 – 4.18 (m, 2H), 3.91 – 3.87 (m, 1H), 2.27 (s,
3H), 1.26 (t, J = 7.2 Hz, 3H), 0.93 (s, 9H), 0.61 (s, 6H); 13C-NMR (150.8 MHz, CDCl3): δ = 172.5, 169.6, 144.8, 141.6, 130.3, 129.8, 129.1, 128.5,
O
O
NH
HN
OO
HN
OMe
OMe
MeO
NH
HN
O
O
OEt
HN
NH
HN
O
O
OEt
NSi
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12
122.0, 120.1, 118.8, 115.2, 114.3, 113.9, 61.3, 57.8, 41.2, 26.3, 20.4, 19.4, 14.1, –4.0; IR
(neat): ν = 3457, 3020, 2402, 1742, 1678, 1512, 1384, 1215, 759, 669; MS-EI: m/z(%): 349.4
(100%, M+ – CONHCH2CO2Et), 479.4 (M+, 20%), 480.4 (M++1, 13%).
Ethyl 2-(2-(6-methyl-1H-indol-3-yl)-2-(p-tolylamino)acetamido)acetate: 48h, 62% yield, 1H-NMR (600 MHz, CDCl3): δ = 8.27 (br, 1H), 7.63 – 6.60
(m, 9H), 5.06 (s, 1H), 4.31 – 4.27 (m, 1H), 4.20 – 4.16 (m,
2H), 3.91 – 3.87 (m, 1H), 2.44 (s, 3H), 2.27 (s, 3H), 1.26
(t, J = 7.2 Hz, 1H), 0.93 (s, 9H), 0.61 (s, 6H); 13C-NMR
(150.8 MHz, CDCl3): δ = 172.7, 169.8, 144.8, 136.9, 132.5,
129.8, 128.5, 123.6, 122.8, 121.9, 118.4, 113.9, 113.1, 111.5, 61.4, 57.7, 41.2, 20.4, 14.2,
14.1; IR (neat): ν = 3379, 2982, 2924, 2865, 1740, 1664, 1518, 1453, 1382, 1300, 1209, 860,
807, 755, 587, 507; MS-EI: m/z(%): 249.3 (100%, M+ – CONHCH2CO2Et), 379.3 (M+, 6%),
380.3 (M++1, 2%).
Isopropyl 2-(2-(1H-indol-3-yl)-2-(p-tolylamino)acetamido)acetate: 48h, 63% yield, 1H-
NMR (400 MHz, CDCl3): δ = 8.50 (br, 1H), 7.66 – 6.60 (m,
10H), 5.09 (s, 1H), 5.08 – 5.02 (m, 1H), 4.30 – 4.24 (m, 1H),
3.89 – 3.83 (m, 1H), 2.27 (s, 3H), 1.23 (t, J = 5.6 Hz, 6H); 13C-NMR (100.6 MHz, CDCl3): δ = 172.7, 169.3, 144.8,
136.4, 129.9, 128.5, 125.7, 123.5, 122.5, 120.1, 118.7, 113.9,
113.2, 111.6, 69.3, 57.6, 41.4, 21.7, 20.4; IR (neat): ν = 3379, 2982, 2928, 2868, 1733, 1664,
1519, 1459, 1378, 1217, 1106, 814, 750, 504; MS-EI: m/z(%): 235.4 (100%, M+ –
CONHCH2CO2iPr), 379.4 (M+, 8%), 380.4 (M++1, 2%).
Isopropyl 2-(2-(5-bromo-1-methyl-1H-indol-3-yl)-2-(p-tolylamino)acetamido)acetate:
48h, 51% yield, 1H-NMR (400 MHz, CDCl3): δ = 7.41 –
7.31 (m, 1H), 7.58 – 6.59 (m, 7H), 5.08 – 5.02 (m, 1H),
5.00 (s, 1H), 4.28 – 4.22 (m, 1H), 3.87 – 3.82 (m, 1H),
3.72 (s, 3H), 2.56 (s, 3H), 1.22 (t, J = 5.6 Hz, J = 5.6 Hz,
6H); 13C-NMR (100.6 MHz, CDCl3): δ = 172.4, 169.0,
144.8, 137.6, 136.0, 131.7, 129.8, 129.0, 128.5, 128.4, 126.2, 122.6, 120.4, 120.0, 114.0,
111.3, 109.4, 69.2, 57.3, 41.6, 21.7, 20.4; IR (neat): ν = 3373, 2980, 2927, 2022, 1736, 1670,
1517, 1472, 1378, 1296, 1212, 1106, 1035, 940, 755; MS-EI: m/z(%): 327.3 (100%, M+ –
CONHCH2CO2iPr), 471.3 (M+, 7%), 472.3 (M++1, 2%).
NH
HN
O
O
OEt
HN
NH
HN
O
O
OiPr
HN
NH
HN
O
O
OiPr
NBr
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Isopropyl 2-(2-(2-phenyl-1H-indol-3-yl)-2-(p-tolylamino)acetamido)acetate: 48h, 50%
yield, 1H-NMR (400 MHz, CDCl3): δ = 8.44 (br, 1H),
7.89 – 7.84 (m, 2H), 7.76 – 7.74 (m, 2H), 7.42 – 7.15
(m, 6H), 6.99 – 6.97 (m, 2H), 6.56 – 6.54 (m, 2H), 5.16
(s, 1H), 5.09 – 5.03 (m, 1H), 4.42 (br, 1H), 4.17 – 4.11
(m, 1H), 3.99 – 3.93 (m, 1H), 2.23 (s, 3H), 1.22 (t, J =
5.6 Hz, 6H); 13C-NMR (100.6 MHz, CDCl3): δ = 172.4, 169.0, 144.7, 137.6, 136.0, 131.7,
129.8, 129.0, 128.9, 128.5, 128.4, 126.2, 122.6, 120.4, 120.0, 114.0, 111.3, 109.4, 69.2, 57.3,
41.6, 21.7, 20.4; IR (neat): ν = 3464, 2922, 2861, 2442, 1949, 1734, 1663, 1616, 1382, 1100,
1023, 935, 683; MS-EI: m/z(%): 311.3 (100%, M+ – CONHCH2CO2iPr), 455.3 (M+, 15%),
456.3 (M++1, 6%).
Ethyl 2-(2-(7-methyl-1H-indol-3-yl)-2-(p-tolylamino)acetamido)acetate: 48h, 76% yield, 1H-NMR (400 MHz, CDCl3): δ = 8.34 (br, 1H), 7.65 – 7.62
(m, 1H), 7.49 – 7.32 (m, 2H), 7.07 – 6.60 (m, 6H), 5.09 (s,
1H), 4.32– 4.26 (m, 1H), 4.21 – 4.15 (m, 2H), 3.92 – 3.86
(m, 1H), 2.46 (s, 3H), 2.27 (s, 3H), 1.24 (t, J = 7.2 Hz, 3H); 13C-NMR (100.6 MHz, CDCl3): δ = 172.7, 169.7, 144.8,
136.0, 129.8, 128.5, 125.3, 123.2, 123.1, 120.8, 120.4, 116.4, 113.9, 113.7, 61.4, 57.8, 41.2,
20.4, 16.5, 14.1; IR (neat): ν = 3391, 2921, 2857, 2421, 2232, 1738, 1663, 1517, 1443, 1384,
1208, 1103, 1026, 809, 753; MS-EI: m/z(%): 249.5 (100%, M+ – CONHCH2CO2Et), 379.5
(M+, 17%), 380.5 (M++1, 12%).
Methyl 2-(2-(1H-indol-3-yl)-2-(p-tolylamino)acetamido)acetate: 48h, 66% yield, 1H-NMR
(400 MHz, CDCl3): δ = 8.47 (br, 1H), 7.67 – 7.61 (m,
2H), 7.37 – 6.61 (m, 8H), 5.09 (s, 1H), 4.34 – 4.27 (m,
1H), 3.93 – 3.87 (m, 1H), 3.72 (s, 3H), 2.27 (s, 3H); 13C-
NMR (100.6 MHz, CDCl3): δ = 172.8, 170.2, 144.7,
136.4, 129.9, 128.6, 125.7, 123.5, 122.6, 120.1, 118.7,
113.9, 113.1, 111.6, 57.7, 52.3, 41.0, 20.4; IR (neat): ν = 3380, 3013, 2924, 2859, 2131, 1744,
1664, 1618, 1518, 1439, 1381, 1216, 1108, 1012, 812, 751; MS-EI: m/z(%): 235.3 (100%, M+
– CONHCH2CO2Me), 351.3 (M+, 11%), 352.3 (M++1, 3%).
NH
HN
O
O
OiPr
HN
Ph
NH
HN
O
O
OEt
HN
NH
HN
O
O
OMe
HN
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14
Ethyl 2-(2-(2-phenyl-1H-indol-3-yl)-2-(p-tolylamino)acetamido)acetate: 48h, 52% yield, 1H-NMR (400 MHz, CDCl3): δ = 8.39 (br, 1H), 7.88 – 7.85
(m, 2H), 7.77 – 7.35 (m, 6H), 7.24 – 6.54 (m, 6H), 5.16 (s,
1H), 4.41 (br, 1H), 4.20 – 4.16 (m, 2H), 4.15 – 4.13 (m,
1H), 4.03 – 3.97 (m, 1H), 2.23 (s, 3H), 1.23 (t, J = 7.2 Hz,
3H); 13C-NMR (100.6 MHz, CDCl3): δ = 172.5, 169.5,
144.7, 137.6, 136.0, 131.7, 129.7, 129.0, 128.9, 128.5, 128.4, 126.1, 122.6, 120.3, 120.0,
114.0, 111.3, 109.4, 61.4, 57.3, 41.4, 20.4, 14.1; IR (neat): ν = 3374, 2924, 2523, 1887, 1738,
1667, 1516, 1455, 1382, 1213, 1116, 1023, 923, 809, 752, 701, 507; MS-EI: m/z(%): 311.4
(100%, M+ – CONHCH2CO2Et), 441.5 (M+, 15%).
Ethyl 2-(2-(5-bromo-1-methyl-1H-indol-3-yl)-2-(p-tolylamino)acetamido)acetate: 48h,
55% yield, 1H-NMR (400 MHz, CDCl3): δ = 7.75 – 7.74
(m, 1H), 7.62 – 7.27(m, 3H), 7.19 – 6.60 (m, 5H), 5.01 (s,
1H), 4.33 – 4.27 (m, 1H), 4.23 – 4.18 (m, 2H), 3.92 – 3.85
(m, 1H), 3.74 (s, 3H), 2.27 (s, 3H), 1.26 (t, J = 7.2 Hz, 3H); 13C-NMR (100.6 MHz, CDCl3): δ = 172.3, 169.6, 144.5,
135.9, 129.9, 129.0, 128.7, 127.9, 125.1, 121.5, 113.9, 113.3, 111.5, 111.1, 61.5, 57.3, 41.2,
33.1, 20.4, 14.1; IR (neat): ν = 3401, 3019, 2924, 2402, 1740, 1676, 1516, 1471, 1383, 1215,
1024, 928, 759, 670; MS-EI: m/z(%): 327.3 (100%, M+ – CONHCH2CO2Et), 457.4 (M+
(Br79), 15%), 459.4 (M+ (Br81), 17%).
References:
[1] J. Xie, Z.-Z. Huang, Angew. Chem. Int. Ed. 2010, 49, 10181.
[2] L. Zhao, O. Basle, C.-J. Li, Proc. Natl. Acad. Sci. USA. 2009, 106, 4106.
[3] L. Zhao, C.-J. Li, Angew. Chem. Int. Ed. 2008, 47, 7075.
[4] M. Soueidan, J. Collin, R. Gil, Tetrahedron Lett, 2006, 47, 5467.
NH
HN
O
O
OEt
HN
Ph
NH
HN
O
O
OEt
NBr
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
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