N. Jacobi, T. Lindel
FULL PAPER
(t, J = 6.8 Hz, 1 H, CCHCH2), 5.13 (br. s, 4 H, NH2), 4.21 (d, J
= 6.8 Hz, 2 H, CCHCH2), 3.35 (s, 3 H, OCH3), 2.97 [s, 6 H,
N(CH3)2], 2.92 [s, 6 H, N(CH3)2] ppm. 13C NMR (150 MHz,
CDCl3): δ = 147.8 (CNH2), 147.5 (CNH2), 137.0 (NCHCN), 133.6
3
3
Honeywell Specialty Chemicals Seelze GmbH (Seelze, Germany)
are thanked for the donation of solvents.
(NCHCN), 127.6 (CCHCH2), 126.3 (CCHCH2), 112.9 (NCHCN), [1] A. Al-Mourabit, P. Potier, Eur. J. Org. Chem. 2001, 237–243.
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111.6 (NCHCN), 69.5 (OCH2), 58.0 (OCH3), 38.7 [2 C, N(CH3)2],
38.7 [2 C, N(CH3)2] ppm. MS (ESI+): m/z (%) = 471 (100) [M +
Na]+, 449 (53) [M + H]+, 417 (80) [M – OCH3]+. HRMS (ESI):
calcd. 449.1384 (C H N O S ); found 449.1380. IR (ATR): ν =
˜
14 25
8
5 2
3441 (w), 2922 (w), 1636 (m), 1379 (m), 1266 (w), 1172 (m), 1053
(m), 964 (m), 717 (s), 600 (s) cm–1. UV (MeOH): λmax (lgε) = 260
(3.85), 213 (4.17), 203 nm (4.23).
4,4Ј-(3-Methoxyprop-1-ene-1,1-diyl)bis(2-azido-1H-imidazole) (41):
To a solution of the protected azide 39 (396.0 mg, 0.791 mmol) in
MeOH (10 mL) was added an excess of concd. HCl (5 mL) and the
reaction mixture was refluxed for 3 h. The reaction mixture was
concentrated and the residue was purified by column chromatog-
raphy (silica, CHCl3/MeOH/NH3, 90:10:1) to give the deprotected
azide 41 (163.0 mg, 72%) as a colorless solid. Rf (CHCl3/MeOH/
1
NH3, 90:10:1) = 0.34. H NMR (400 MHz, CD3OD): δ = 6.91 (s,
1 H, NHCH), 6.73 (s, 1 H, NHCH), 6.28 (br. s, 1 H, CCH), 4.16
[7] A. Arrki, M. Tsuda, T. Kubota, Y. Mikami, J. Fromont, J. Ko-
bayashi, Org. Lett. 2007, 9, 2369–2371.
3
(d, J = 4.5 Hz, 2 H, CH2), 3.33 (s, 3 H, OCH3) ppm. 13C NMR
(100 MHz, CD3OD):
δ = 144.1 (CN3), 142.5 (CN3), 130.5
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I. B. Seiple, I. S. Young, P. S. Baran, J. Am. Chem. Soc. 2008,
130, 16490–16491.
(NHCHCN), 127.3 (CCHCH2), 127.2 (NHCHCN), 124.3
(CCHCH2), 116.8 (NHCHCN), 115.5 (NHCHCN), 70.7 (CH2),
58.2 (OCH3) ppm. MS (ESI+): m/z (%) = 309 (100) [M + Na]+,
595 (28) [2M
+
Na]+. HRMS (ESI): calcd. 309.0931
(C H N NaO); found 309.0930. IR (ATR): ν = 3133 (w), 2124
˜
10 10 10
(s), 1524 (m), 1498 (w), 1459 (w), 1148 (m), 1076 (m), 771 (m) cm–1.
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1322.
UV (MeOH): λmax (lgε) = 272 (4.23), 202 nm (4.04).
4,4Ј-(3-Methoxyprop-1-ene-1,1-diyl)bis(1H-imidazol-2-amine) (42):
Diazide 41 (137.0 mg, 0.479 mmol) was dissolved in MeOH (5 mL)
in presence of Lindlar catalyst (Pd/CaCO3 with 5% Pb, 5% Pd,
102 mg, 0.048 mmol Pd). After stirring at room temp. under 1 atm
H2 for 4 h, the reaction mixture was filtered through a pad of Celite
and the filtrate was concentrated. The residue was purified by col-
umn chromatography (RP18, MeOH/H2O/0.5% TFA, 1:6) to give
diamine 42 (97.0 mg, 86%) as a yellow oil. Rf (RP18, MeOH/H2O,
1:6) = 0.50. 1H NMR (600 MHz, CD3OD): δ = 6.94 (s, 1 H,
3
NH2CNCH), 6.78 (s, 1 H, NH2CNHCH), 6.31 (t, J = 6.6 Hz, 1
3
H, CHCH2OCH3), 4.11 (d, J = 6.6 Hz, 2 H, CH2OCH3), 3.36 (s,
3 H, OCH3) ppm. 13C NMR (150 MHz, CD3OD): δ = 149.9
(CNH2), 149.4 (CNH2), 129.7 (CHCH2OCH3), 127.5 (CH2CHC),
121.7 (CH2CHCC), 120.5 (CH2CHCC), 115.3 (NH2CNCH), 113.6
(NH2CNHCH), 69.7 (CH2OCH3), 58.6 (OCH3) ppm. MS (ESI+):
m/z (%) = 235 (13) [M + H]+, 203 (100), 201 (30). HRMS (ESI):
calcd. 235.1302 (C H N O); found 235.1302. IR (ATR): ν = 3153
˜
10 15
6
(m), 1669 (s), 1181 (s), 1129 (s), 837 (m), 799 (m), 720 (m) cm–1.
UV (MeOH): λmax (lgε) = 354 (2.97), 265 (3.48), 203 nm (3.76).
Supporting Information (see also the footnote on the first page of
this article): NMR spectra of compounds 8–18, 20, 22, 24–32, 34–
43, NOESY spectra of compounds 29, 42.
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Acknowledgments
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b) L. Zhou, K. M. Nicholas, Inorg. Chem. 2008, 47, 4356–4367.
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J. J. Piwinski, P. C. Ting, M. M. Albanese, M. Y. Berlin, X.
Zhu, S.-C. Wong, S. B. Rosenblum, Y. Jiang, R. West, S. She,
Financial support of this research by the Deutsche Forschungsge-
meinschaft (DFG), Li 597/5-1) is gratefully acknowledged. Lars
Henneicke is thanked for laboratory assistance. Benjamin Troegel
is thanked for the synthesis of 20 and 22. We also thank Merck
KGaA (Darmstadt, Germany) for the generous gift of chromatog-
raphy materials. BASF Group (Ludwigshafen, Germany) and
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Eur. J. Org. Chem. 2010, 5415–5425