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New Journal of Chemistry
Page 8 of 10
DOI: 10.1039/C7NJ05020H
ARTICLE
Journal Name
butoxycarbonyl)amino)ferrocene-1-carboxylic anhydride (14, 23 FcCH), 69.9 (2 x FcCH), 65.2 (CH2), 63.6 (FcC), 61.4 (2 x FcCH), 46.7
mg, 7%) as a red solid. 1’-((tert-Butoxycarbonyl)amino)ferrocene- (CH), 25.4 (2 x CH2). Anal. Calcd for C30H24FeN2O6: C, 63.85; H, 4.29;
1-carboxylic anhydride
(ATR): 3316, 2979, 1762, 1706, 1688, 1552, 1389, 1368, 1356, 2,5-Dioxopyrrolidin-1-yl 1’-((allyloxycarbonyl)amino)ferrocene -
(
14): mp 165-167 °C (lit.24 167-168 °C); IR N, 4.96. Found: C, 63.97; H, 4.40; N, 5.07.
1239, 1161, 1065, 1041, 1002, 905, 878, 825, 755 cm-1; 1H NMR 1-carboxylate
(500 MHz, CDCl3) 6.36 (s, 2H, 2 x NH), 4.82 (s, 4H, 4 x FcCH), 4.68 ((allyloxycarbonyl)amino)ferrocene-1-carboxylic acid (
(s, 4H, 4 x FcCH), 4.56 (s, 4H, 4 x FcCH), 4.08 (s, 4H, 4 x fcCH), 1.43 0.12 mmol, 1.0 equiv), N-hydroxysuccinimide (34.5 mg, 0.18
(13
).
The general procedure
2
using 1’-
9, 49.4 mg,
δ
(s, 18H, 2 x C(CH3)3; 13C NMR (125.7 MHz, CDCl3)
δ
168.6 (2 x mmol, 1.5 equiv) and EDC.HCl (20.7 mg, 0.18 mmol, 1.5 equiv)
C=Oanhydride), 153.5 (C=Ocarbamate), 99.0 (2 x FcC), 80.4 (2 x C(CH3)3), afforded the title product as an orange solid (47.7 mg, 74%). mp
74.2 (4 x FcCH), 72.2 (4 x fcCH), 70.1 (2 x FcCH), 66.3 (4 x FcCH), 80-84 °C; IR (ATR): 3331, 1760, 1722, 1548, 1446, 1372, 1264,
62.4 (4 x FcCH), 28.5 (2 x C(CH3)3). 2,5-Dioxopyrrolidin-1-yl 1’- 1233, 1201, 1070, 988, 933, 885, 816, 747 cm-1; 1H NMR (500 MHz,
(tert-butoxycarbonyl amino)ferrocene-1-carboxylate
( δ 8.97 (s, 1H, NH), 5.95 (m, 1H, HC=CHH), 5.33 (d, J =
10): mp DMSO-d6)
112-116 °C; IR (ATR): 3357, 1761, 1723, 1539, 1444, 1367, 264, 17.3 Hz, 1H, HC=CHH), 5.23 (d, J = 10.3 Hz, 1H, HC=CHH), 4.89 (s,
1242, 1206, 1158, 1070, 981, 879, 822, 746 cm-1; 1H NMR (500 2H, 2 x FcCH), 4.63 (s, 2H, 2 x FcCH), 4.59 (s, 2H, 2 x FcCH), 4.57 (s,
MHz, DMSO-d6)
δ
8.56 (br s, 1H, NH), 4.87 (s, 2H, 2 x FcCH), 4.60 2H, CH2), 4.22 (s, 2H, 2 x FcCH), 2.86 (s, 4H, 2 x CH2); 13C NMR
(br s, 2 H, 2 x FcCH), 4.57 (s, 2H, 2 x FcCH), 4.19 (s, 2H, 2 x FcCH), (125.7 MHz, DMSO-d6)
2.86 (s, 4H, 2 x CH2), 1.45 (s, 9H, C(CH3)3); 13C NMR (125.7 MHz, 153.3 (C=Ocarbamate), 133.3 (HC=CH2), 117.3 (HC=CH2), 99.3 (FcC),
DMSO-d6)
170.6 (C=Osuccinimidyl), 166.9 (C=Oester), 152.8 75.0 (2 x FcCH), 70.8 (2 x FcCH), 67.0 (2 x FcCH), 64.7 (CH2), 63.7
δ 170.6 (C=Osuccinimidyl), 166.9 (C=Oester),
δ
(C=Ocarbamate), 99.8 (FcC), 78.8 (C(CH3)3), 74.9 (2 x FcCH), 70.6 (2 x (FcC), 61.5 (2 x FcCH), 25.5 (2 x CH2). Anal. Calcd for C19H18FeN2O6:
FcCH), 66.9 (2 x FcCH), 63.5 (FcC), 61.4 (2 x FcCH), 28.0 (C(CH3)3), C, 53.54; H, 4.26; N, 6.57. Found: C, 53.63; H, 4.38; N, 6.68.
25.5 (2 x CH2). Anal. Calcd for C20H22FeN2O6: C, 54.32; H, 5.01; N, N-methyl
6.33. Found: C, 54.40; H, 5.11; N, 6.45. Crystal data for 10. carboxamide
C20H22FeN2O6, M = 442.24, T = 150(2) K, monoclinic P 21/c, a = 0.3 mmol, 1.6 equiv) was added to
1’-((tert-butoxycarbonyl)amino)ferrocene-1-
(
15
).
Under argon, triethylamine (44.6 μL, 32.3 mg,
a solution of 2,5-
21.3600(13), b = 10.0652(5), c = 9.5245(6) Å, β = 96.112(2) °, V = dioxopyrrolidin-1-yl 1’-(tert-butylcarbonylamino)ferrocene-1-
2036.1(2) Å3. Z = 4, d = 1.443 g.cm-3, μ = 0.780 mm-1. A final carboxylate (10, 88.5 mg, 0.2 mmol, 1.0 equiv) and methylamine
refinement on F2 with 4645 unique intensities and 265 parameters hydrochloride (26.1 mg, 0.3 mmol, 1.6 equiv) in anhydrous THF
converged at wR(F2) = 0.1664 (R(F) = 0.0620) for 3849 observed (0.8 mL) and the reaction mixture was stirred at rt overnight.
reflections with I > 2σ(I). CCDC 1584019.
2,5-Dioxopyrrolidin-1-yl 1’-((benzyloxycarbonyl)amino)ferrocene- with heptane/EtOAc (50:50 to 30:70) afforded the title product as
1-carboxylate 11 The general procedure using 1’- an orange solid (66.9 mg, 93%). mp 70-80 °C; IR (ATR): 3290 (br),
((benzyloxycarbonyl)amino)ferrocene-1-carboxylic acid 45.5 2975 (br), 1694, 1627, 1547, 1388, 1365, 1245, 1158, 1068, 1019,
mg, 0.12 mmol, 1.0 equiv), N-hydroxysuccinimide (34.5 mg, 0.18 939, 879, 813, 755 cm-1; 1H NMR (500 MHz, DMSO-d6)
8.39 (s,
Direct purification by column chromatography on silica, eluting
(
).
2
(7,
δ
mmol, 1.5 equiv) and EDC.HCl (20.7 mg, 0.18 mmol, 1.5 equiv) 1H, NHamide), 7.61 (s, 1H, NHcarbamate), 4.66 (s, 2H, 2 x FcCH), 4.43 (s,
afforded the title product as an orange solid (49.0 mg, 86%). mp 2H, 2 x FcCH), 4.21 (s, 2H, 2 x FcCH), 3.87 (s, 2H, 2 x FcCH), 2.69 (s,
70-74 °C; IR (ATR): 3316, 1760, 1722, 1550, 1446, 1373, 1264, 3H, CH3), 1.44 (s, 9H, C(CH3)3); 13C NMR (125.7 MHz, DMSO-d6)
δ
1232, 1200, 1069, 1028, 986, 884,816, 744, 697 cm-1; 1H NMR (500 169.1 (C=Oamide), 153.0 (C=Ocarbamate), 98.0 (FcC), 78.5 (C(CH3)3),
MHz, DMSO-d6)
9.02 (s, 1H, NH), 7.40 (s, 4H, 4 x ArCH), 7.34 (s, 77.5 (FcC), 70.7 (2 x FcCH), 68.6 (2 x FcCH), 65.1 (2 x FcCH), 60.8 (2
1H, ArCH), 5.12 (s, 2H, CH2), 4.87 (s, 2H, 2 x FcCH), 4.63 (s, 2H, 2 x x FcCH), 28.1 (C(CH3)3), 25.9 (CH3). Anal. Calcd for C17H22FeN2O3: C,
δ
FcCH), 4.56 (s, 2H, 2 x FcCH), 4.22 (s, 2H, 2 x FcCH), 2.84 (s, 4H, 2 x 57.00; H, 6.19; N, 7.82. Found: C, 57.09; H, 6.30; N, 7.94.
CH2); 13C NMR (125.7 MHz, DMSO-d6)
δ 170.6 (C=Osuccinimidyl), 166.9
(C=Oester), 153.5 (C=Ocarbamate), 136.7 (ArC), 128.4 (2 x ArCH), 128.0
(ArCH), 127.9 (2 x ArCH), 99.2 (FcC); 75.0 (2 x FcCH), 70.8 (2 x
FcCH), 67.0 (2 x FcCH), 65.8 (CH2), 63.7 (FcC), 61.5 (2 x FcCH), 25.5
(2 x CH2). Anal. Calcd for C23H20FeN2O6: C, 58.00; H, 4.23; N, 5.88.
Found: C, 58.09; H, 4.29; N, 5.99.
Conflicts of interest
There are no conflicts to declare.
2,5-Dioxopyrrolidin-1-yl
yl)methoxycarbonyl)amino]ferrocene-1-carboxylate
general procedure using 1’-[((fluoren-9-
yl)methoxycarbonyl)amino]ferrocene-1-carboxylic acid 56.1
1’-[((fluoren-9-
Acknowledgements
(
12 The
).
2
This work was supported by the Université de Rennes 1. We
acknowledge FEDER founds (D8 VENTURE Bruker AXS
diffractometer). W. E. would like to thank J. Mongin for
technical assistance and Prof. F. Mongin for critically reviewing
this document and for making valuable suggestions.
(8,
mg, 0.12 mmol, 1.0 equiv), N-hydroxysuccinimide (34.5 mg, 0.18
mmol, 1.5 equiv) and EDC.HCl (20.7 mg, 0.18 mmol, 1.5 equiv)
afforded the title product as an orange solid (59.9 mg, 88.5%). mp
80-84 °C; IR (ATR): 3253, 1760, 1724, 1551, 1447, 1373, 1233,
1203, 1071, 986, 884, 741 cm-1; 1H NMR (500 MHz, DMSO-d6)
δ
8.98 (br s, 1H, NH), 7.91 (d, J = 6.9 Hz, 2H, 2 x ArCH), 7.73 (d, J =
6.9 Hz, 2H, 2 x ArCH), 7.43 (t, J = 6.9 Hz, 2H, 2 x ArCH), 7.36 (t, J =
6.9 Hz, 2H, 2 x ArCH), 4.85 (s, 2H, 2 x FcCH), 4.63 (s, 2H, 2 x FcCH),
4.50 (s, 4H, 2 x FcCH, CH2), 4.29 (s, 1H, CH), 4.21 (s, 2H, 2 x FcCH),
References
1.
R. S. Herrick, R. M. Jarret, T. P. Curran, D. R. Dragoli, M. B.
Flaherty, S. E. Lindyberg, R. A. Slate and L. C. Thornton,
Tetrahedron Lett., 1996, 37, 5289-5292.
2.85 (s, 4H, 2 x CH2); 13C NMR (125.7 MHz, DMSO-d6)
δ 170.6
(C=Osuccinimidyl), 166.8 (C=Oester), 153.3 (C=Ocarbamate), 143.7 (2 x ArC),
140.8 (2 x ArCH), 127.6 (2 x ArCH), 127.0 (2 x ArCH), 125.0 (2 x
ArCH), 120.1 (2 x ArCH), 99.2 (FcC), 74.9 (2 x FcCH), 70.7 (2 x
2.
A. Lataifeh, S. Beheshti and H.-B. Kraatz, Eur. J. Inorg.
Chem., 2009, 2009, 3205-3218.
8 | J. Name., 2012, 00, 1-3
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