C. Frixa et al. / Tetrahedron Letters 43 (2002) 1557–1559
1559
require the iodoarene which, in this case, is consumed
in a side-reaction. Direct replacement of iodine with
chlorine on a benzene ring with CuCl at high tempera-
m, 3×Ph 3,4,5-H ), 7.96 (2H, d, J=8.2 Hz, Ar 2,6-H ),
3
2
8.09 (2H, d, J=8.2 Hz, Ar 3,5-H ), 8.22 (6H, d, J=7.5
2
Hz, 3×Ph 2,6-H ), 8.93 (2H, d, J=4.8 Hz) and 8.96 (2H,
2
2
3,24
tures has been reported previously
but it is interest-
d, J=4.8 Hz) (2,3,7,8-H ), 8.95 (4H, s, 12,13,17,18-H );
4
4
6
8
ing to note that such replacement only takes place on
the copper complex whereas 6 contains only zinc.
MS (FAB) m/z 807.0559 (M+H) (C H N I Zn requires
807.0607), 805.0579 (M+H) (C H N I Zn requires
44 28 4
05.0619), 803.0610 (M+H) (C H N I Zn requires
44 28 4
6
6
6
4
8
44 28 4
Although this process requires further optimisation, it
represents the first direct coupling of a carborane with
a porphyrin via a carbonꢀcarbon bond. As such, it
provides an opportunity for access to tumour-targeted
carboranylporphyrins for therapeutic applications.
803.0650).
16. Vinas, C.; Benakki, R.; Teixidor, F.; Casabo, J. Inorg.
Chem. 1995, 34, 3844.
17. Coupling reaction: sec-BuLi (780 mmol) was stirred with
1,2-dicarbaclosododecaborane(12) (750 mmol) in bis(2-
methoxyethyl)ether (3 mL) at −78°C for 5 min. The
mixture was warmed to 20°C for 40 min before CuCl (1.0
mmol) was added. After 2 h, pyridine (450 mL) was
added. After a further 2 h, 5 (250 mg, 310 mmol) was
added; the mixture was boiled under reflux for 12 days.
Acknowledgements
The authors thank Mr. R. R. Hartell and Mr. D. J.
Wood for the NMR spectra and Mr. C. Cryer for the
mass spectra. We are grateful to Scotia Pharmaceuticals
for donation of some materials. C.F. held a Research
Studentship from the Department of Pharmacy & Phar-
macology, University of Bath.
Evaporation and chromatography (hexane/CHCl , 2:1
3
3:4) gave 7 (65%) (purple crystals); mp >350°C. Further
elution gave 6 (8%) as a purple solid; mp >350°C; lH
(CDCl ) 2.4 (10H, brq, J =145 Hz, B H ), 4.29 (1H,
3
B–H
10 10
brs, carborane 2-H), 7.75 (9H, m, 3×Ph 3,4,5-H ), 7.86
3
(2H, d, J=8.5 Hz, Ar 2,6-H ), 8.17 (2H, d, J=8.5 Hz, Ar
2
3
,5-H ), 8.21 (6H, m, 3×Ph 2,6-H ), 8.83 (2H, d, J=4.4
2
2
Hz) and 8.94 (6H, m) (2,3,7,8,12,13,17,18-H ); MS (FAB)
8
0 11 68
1
46 39 4 9
References
m/z (all M+H) 824.3387 (C H N B B Zn requires
66
824.3390),
823.3359
(C H N B Zn
requires
4
6
39
4
0 11 66
10
1
1
. Soloway, A. H.; Tjarks, W.; Barnum, B. A.; Rong, F.-G.;
Barth, R. F.; Codogni, I. M.; Wilson, J. G. Chem. Rev.
823.3366), 822.3384 (C H N B B Zn requires
46
39
4
9
65
822.3402),
821.3382
(C H N B Zn
requires
4
6
39
4 10
0 11 65
1
1
998, 98, 1515.
821.3397), 820.3408 (C H N B B9 Zn requires
46
39
4
2
3
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18. Crystal data: C H ClCuN , M=707.66, wavelength=
44
24
4
1
997, 26, 231.
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008.
0.71073
A
,
,
orthorhombic, space group F2dd, a=
4
5
6
14.1650(9), b=21.3960(13), c=21.600(2) A
,
, U=6546.4(8)
3
−3
−1
7
A , Z=8, Dcalcd=1.436 mg m , v=0.789 mm ,
,
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M.-S.; Kaye, A. H. Proc. Natl. Acad. Sci. USA 1995, 92,
F(000)=2896, crystal size 0.20×0.08×0.08 mm, unique
reflections=2220 [R(int)=0.0833], observed I>2|(I)=
1863, R =0.0608, wR =0.1046 (observed data), max.
1
2
−
3
peak/hole 0.211 and −0.341 e A
and refinement completed using SHELXS-86,
,
. Structural solution
19
1
2126.
2
0
21
7
. Hill, J. S.; Kahl, S. B.; Kaye, A. H.; Stylli, S. S.; Koo,
M.-S.; Gonzales, M. F.; Vardaxis, N. J.; Johnson, C. I.
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8
9
. Vicente, M. G. H.; Shetty, S. J.; Wickramasinghe, A.;
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22. Crystallographic data (excluding structure factors) for the
structure in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supplemen-
tary publication number CCDC 173872. Copies of the
data can be obtained, free of charge, on application to
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax:
+44 (0) 1223-336033 or e-mail: deposit@ccdc.cam.
ac.uk].
1
0. Lauceri, R.; Purrello, R.; Shetty, S. J.; Vicente, M. G. H.
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1
5. Selected spectroscopic data for 5: lH (CDCl ) 7.76 (9H,
1958, 80, 1716.
3