RSC Advances
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ARTICLE
DOI: 10.1039/C4RA09605C
General Procedure 3 - Alkene Reduction
Bag, 1797, Penrith South DC, Australia, Eꢀmail:
c.gordon2@uws.edu.au, Fax: +61 (02) 4620 3025, Tel: +61
Norcantharidin (31). A solution of 5,6ꢀnorcantharidin (30
)
(0.20 g, 1.2 mmol) was diluted in MeOH (24 mL) to afford a (02) 4620 3201
0.05 M solution which was subsequently hydrogenated with a
HꢀCube™ using a 5% Pt/C (sulfided) catalyst at 1 mL.minꢀ1
flow rate, 30°C and 30 bar 10% H2 pressure. After completion
of the reaction, the solvent was removed in vacuo to afford
norcantharidin 31 as a white solid (0.20 g, 100%); mp 115 °C.
LRMS (ESI+) m/z 267 (M+1). 1H NMR (CDCl3, 400 MHz) δ
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5
5.06 (dd,
J = 3.2, 2.2 Hz, 1H), 3.20 (s, 1H), 1.99 – 1.83 (m,
1H), 1.75 – 1.55 (m, 1H). 13C NMR (CDCl3, 101 MHz): δ
171.15, 80.18, 50.58, 28.15.
8
3-((4-bromobenzyl)carbamoyl)-7-
oxabicyclo[2.2.1]heptane-2-carboxylic acid (33). 5,6ꢀ
4
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6389.
norcantharidin
(30) (0.18 g, 1.07 mmol) and 4ꢀ
bromobenzylamine (23) (0.2 g, 1.07 mmol) were dissolved
separately in diethyl ether (10 mL x 2) and the solutions were
added together and the reaction was left to stir at room
temperature for 4 hours. The solution was filtered and washed
with cold diethyl ether and dried under suction to afford 32 as a
white solid. The crude product 32 (0.15 g, 0.74 mmol) was
dissolved in a mixture (1:1) methanol:acetone (6 mL) to afford
a 0.05 M solution which was subsequently hydrogenated with a
HꢀCube™ using a 5% Pt/C (sulfided) catalyst at 1 mL.minꢀ1
flow rate, 30°C and 30 bar H2 pressure. After completion of the
reaction, the eluate was concentrated in vacuo and then
triturated with ether to afford 33 as a white solid (0.32 g,
overall 84 %); mp 180 ꢀ 181 °C. 1H NMR (DMSO, 400 MHz) δ
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3
3, 151–185.
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11.96 (s, 1H), 8.05 (t,
7.22 (d, = 8.3 Hz, 2H), 4.74 (d,
4.3 Hz, 1H), 4.22 (dd, = 15.4, 6.0 Hz, 1H), 4.15 (dd,
5.7 Hz, 1H), 2.92 (d, = 9.7 Hz, 1H), 2.86 (d, = 9.7 Hz, 1H),
J
= 5.8 Hz, 1H), 7.48 (d,
= 3.4 Hz, 1H), 4.51 (d,
= 15.4,
J = 8.3 Hz, 2H),
J
J
J =
15. T. Colacot, Top. Catal., 2008, 48, 91–98.
J
J
J
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Snieckus, Angew. Chemie Int. Ed., 2012, 51, 5062–5085.
J
1.63 – 1.41 (m, 4H).13C NMR (DMSO, 101 MHz): δ 172.9,
172.1, 139.6, 131.5, 129.9, 120.1, 79.2, 77.2, 53.3, 51.8, 42.0,
29.4, 28.9.
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,
2
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,
Acknowledgements
2009, 19, 4781–4785.
This project was supported by the Australian Cancer
Research Foundation, Ramaciotti Foundation and the
Australian Research Council. CPG is the recipient of an ARC
DECRA fellowship. LH acknowledges the receipt of a
Postgraduate Scholarship from the University of Newcastle.
19. C. P. Gordon, N. Byrne, and A. McCluskey, Green Chem., 2010, 12
1000–1006.
,
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Hulsizer, and R. A. Urbanek, Tetrahedron Lett., 2012, 53, 5833–
5836.
21. For further information see:ThalesNano, H-Cube Pro Manual, 2010.
22. C. P. Gordon, L. Hizartzidis, M. Tarleton, J. A. Sakoff, J. Gilbert, B.
Supporting Information Available: Supplementary data (GS MS
chromatographic traces, 1H and 13C NMR spectra) associated
with this article can be found in the online version at:
doi:xxxxxxxxx.
E. Campbell, R. B. Gasser, and A. McCluskey, MedChemComm
2014, , 159–164.
,
5
__________________
Notes and references
aCentre for Chemical Biology, Chemistry Building, School of
Environmental and Life Science, The University of Newcastle,
University Drive, Callaghan NSW 2308 Australia.
bNanoscale Organisation and Dynamics Group, School of
Science and Health, University of Western Sydney, Locked
6 | J. Name., 2012, 00, 1-3
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