M. Beller et al.
1
3
C NMR (75 MHz, CDCl
3
, 300 K): d=160.5 (C2), 159.5 (C2/C4), 114.0
Weinheim, 1979, 333; b) G. P. Ellis, T. M. Romney-Alexander,
(
(
C=N), 110.2 ppm (C5); MS (EI, 70 eV); m/z (%): 105 (80), 78 (70), 51
100); HR-MS: not possible due to low volatility of the compound.
Chem. Rev. 1987, 87, 779.
[6] K. Takagi, T. Okamoto, Y. Sakakibara, S. Oka, Chem. Lett. 1973,
1
471.
Selected analytical data of 2,4,6-tri-(tert-butyl)benzonitrile: H NMR
[
7] D. M. Tschaen, R. Desmond, A. O. King, M. C. Fortin, B. Pipik, S.
King, T. R. Verhoeven, Synth. Commun. 1994, 24, 887.
8] M. Sundermeier, A. Zapf, M. Beller, Eur. J. Inorg. Chem. 2003,
(
300 MHz, CDCl
3
, 300 K): d=7.38 (s, 2H), 1.57 (s, 18H), 1.33 ppm (s,
1
3
9
1
2
H); C NMR (CDCl , 75 MHz, 300 K): d=153.2, 152.6, 119.3, 118.8,
3
[
03.8 (Cipso), 34.0, 33.3, 28.8, 28.1 ppm; HR-MS: calculated for C19H29N:
3
513.
[9] M. Sundermeier, A. Zapf, M. Beller, J. Sans, Tetrahedron Lett. 2001,
2, 6707.
71.22945; found: 271.228865.
1
Selected analytical data of 2,4,6-tri(isopropyl)benzonitrile: H NMR
4
(
300 MHz, CDCl
3
, 300 K): d=6.98 (s, 2H), 3.48 (hept, J=7 Hz, 2H), 2.87
1
3
[10] J. Ramnauth, N. Bhardwaj, P. Renton, S. Rakhit, S. P. Maddaford,
(
hept, J=7 Hz, 1H), 1.24 ppm (d, J=7 Hz, 18H); C NMR (CDCl
3
,
Synlett 2003, 2237.
11] M. Sundermeier, A. Zapf, M. Beller, Angew. Chem. 2003, 115, 1700;
Angew. Chem. Int. Ed. 2003, 42, 1661.
12] M. Sundermeier, S. Mutyala, A. Zapf, A. Spannenberg, M. Beller, J.
Organomet. Chem. 2003, 684, 50.
13] H. R. Chobanian, B. P. Fors, L. S. Lin, Tetrahedron Lett. 2006, 47,
7
5 MHz, 300 K): d=147.9, 147.4, 123.6, 122.3, 34.1, 33.6, 24.1, 23.2 ppm;
[
[
[
[
HR-MS: calculated for C16
H
23N: 229.18250; found: 229.182347.
1
Selected analytical data of 2-isopropylbenzonitrile: H NMR (CDCl
3
,
3
7
1
00 MHz, 300 K): d=7.61 (dd, J=7.6 Hz, J=1.2 Hz, 1H), 7.55 (td, J=
.6 Hz, J=1.2 Hz, 1H), 7.40 (bd, J=7.6 Hz 1H), 7.28 (td, J=7.6 Hz, J=
.2 Hz, 1H), 3.39 (hept, J= Hz, 1H), 1.32 ppm (d, J=6.9 Hz, 6H);
3
303.
1
3
C NMR (CDCl
18.2, 111.7, 32.4 (C
45.08860; found: 145.088320.
3
, 75 MHz, 300 K): d=152.4, 133.0, 132.9, 126.3, 125.9,
14] Recent examples: a) R. S. Jensen, A. S. Gajare, K. Toyota, M. Yoshi-
fuji, F. Ozawa, Tetrahedron Lett. 2005, 46, 8645; b) J. M. Veauthier,
C. N. Carlson, G. E. Collis, J. L. Kiplinger, K. D. John, Synthesis
1
1
a
), 23.2 ppm (CH
3
); HR-MS: calculated for C10H11N:
1
Selected analytical data of 2-amino-5-fluoronicotinonitrile: H NMR
2005, 2683; c) R. Chidambaram, Tetrahedron Lett. 2004, 45, 1441.
À
(
CDCl
3
, 300 MHz, 300 K): d=8.16 (d, J=3 Hz, 1H); 7.46 (dd, J=3 Hz,
[15] The price per mol CN is E 2.4 for K [Fe(CN) ] and E 6.6 for KCN;
4
6
1
3
J=7 Hz, 1H), 5.14 ppm (br s, 2H); C NMR (CDCl
3
, 75 MHz, 300 K):
source Aldrich Chemicals Catalogue 2006.
d=156.2 (C2), 151.9 (C5, JC,F =247 Hz), 141.4 (C6, J=25 Hz), 127.6 (C4,
J=22 Hz), 115.3 (C=N), 90.9 ppm (C3); HR-MS: calculated for
[16] a) T. Schareina, A. Zapf, M. Beller, Chem. Commun. 2004, 1388;
b) T. Schareina, A. Zapf, M. Beller, J. Organomet. Chem. 2004, 689,
4576; c) T. Schareina, A. Zapf, W. Mägerlein, N. Müller, M. Beller,
Tetrahedron Lett. 2007, 48, 1087.
[17] T. Schareina, A. Zapf, M. Beller, Tetrahedron Lett. 2005, 46, 2585.
[18] a) S. A. Weissman, D. Zewge, C. Chen, J. Org. Chem. 2005, 70,
1508; b) O. Grossmann, D. Gelman, Org. Lett. 2006, 8, 1189.
[19] T. Schareina, A. Zapf, W. Mägerlein, N. Müller, M. Beller, Synlett
C
6
H
4
FN
3
: 137.03838; found: 137.038247.
1
Selected analytical data of thiazole-2-carbonitrile: H NMR (CDCl
3
3
,
,
1
3
3
7
00 MHz, 300 K): d=8.09 (s, 1H), 7.74 ppm (s, 1H); C NMR (CDCl
5 MHz, 300 K): d=145.3, 136.7, 125.0, 112.7 ppm; HR-MS: calculated
S: 109.99332; found: 109.993126.
Selected analytical data of isoquinoline-4-carbonitrile: H NMR (CDCl
4 2 2
for C H N
1
3
,
2
007, 555.
3
1
7
7
1
1
00 MHz, 300 K): d=9.43 (s, 1H), 8.91 (s, 1H), 8.19 (dd, J=8.4 Hz, J=
[
[
[
20] J. Zanon, A. Klapars, S. L. Buchwald, J. Am. Chem. Soc. 2003, 125,
Hz, 1H), 8.11 (dt, 1H), 7.95 (ddd, J=8 Hz, J=7 Hz, J=1 Hz, 1H),
1
3
2890.
.80 ppm (ddd, J=8 Hz, J=7 Hz, J=1 Hz, 1H); C NMR (CDCl
3
,
21] H.-J. Cristau, A. Ouali, J.-F. Spindler, M. Taillefer, Chem. Eur. J.
5 MHz, 300 K): d=156.3, 148.4, 134.5, 133.1, 129.2, 128.5, 127.6, 124.1,
2
005, 11, 2483.
15.9, 106.0 ppm; HR-MS: calculated for C10
54.052270.
6 2
H N : 154.05255; found:
22] a) V. Sendra, D. Cannella, B. Bersch, F. Fieschi, S. Menage, D. Las-
coux, J. Coves, Biochemistry 2006, 45, 5557; b) D. Hernandez-
Romero, A. Sanchez-Amat, F. Solano, FEBS Lett. 2006, 273, 257;
c) T. Klabunde, C. Eicken, J. C. Sacchettini, B. Krebs, Nat. Struct.
Biol. 1998, 5, 1084; d) K. Brown, M. Tegoni, M. Prudencio, A. S.
Pereira, S. Besson, J. J. Moura, I. Moura, C. Cambillau, Nat. Struct.
Biol. 2000, 7, 191.
Acknowledgements
The authors thank Dr. W. Baumann, Dr. C. Fischer, Mrs. S. Buchholz,
Mrs. S. Schareina and Ms. K. Reincke for analytical support. Generous
support from the state Mecklenburg-Vorpommern, the BMBF, the Deut-
sche Forschungsgemeinschaft (Leibniz prize), and Saltigo GmbH are
gratefully acknowledged.
[
23] a) E. Fadda, N. Chakrabarti, R. Pomes, J. Phys. Chem. B 2005, 109,
2
2629; b) C. D. Syme, R. C. Nadal, S. E. J. Rigby, J. H. Viles, J. Biol.
Chem. 2004, 279, 18169; c) C. S. Atwood, G. Perry, H. Zeng, Y.
Kato, W. D. Jones, K. Q. Ling, X. D. Huang, R. D. Moir, D. D.
Wang, L. M. Sayre, M. A. Smith, S. G. Chen, A. I. Bush, Biochem-
istry 2004, 43, 560; d) M. Nakamura, T. Nakajima, Y. Ohba, S. Ya-
mauchi, B. R. Lee, E. Ichishima, Biochem. J. 2000, 350, 537; e) L.
Banci, I. Bertini, S. Ciofi-Baffoni, E. Katsari, N. Katsaros, K. Kubi-
cek, S. Mangani, Proc. Natl. Acad. Sci. USA 2005, 102, 3994.
[
1] a) R. C. Larock, Comprehensive Organic Transformations, VCH,
New York, 1989, 819; b) C. Grundmann, in Houben-Weyl: Methoden
der organischen Chemie, Vol. E5 (Ed.: J. Falbe), 4th ed., Georg
Thieme, Stuttgart, 1985, 1313.
[
24] For the application of 1-alkylimidazoles as solubilizing additives see:
a) J. A. Welleman, F. B. Hulsbergen, J. Reedijk, Makromol. Chem.
[
[
2] J. Lindley, Tetrahedron 1984, 40, 1433.
1
981, 182, 785; b) J. Zhou, G. C. Fu, J. Am. Chem. Soc. 2003, 125,
3] For a recent catalytic variant of the Sandmeyer reaction see: I. P.
Beletskaya, A. S. Sigeev, A. S. Peregudov, P. V. Petrovskii, J. Orga-
nomet. Chem. 2004, 689, 3810.
1
2527.
[
25] Initial amination reactions of bromobenzenes in the presence of Cu/
-butylimidazole showed that these catalysts are also active for
1
[
4] For recent examples see: a) A. Martin , N. V. Kalevaru, B. Lücke, J.
Sans, Green Chem. 2002, 4, 481; b) Y. Liu, M. Zhong, W. Yu, Y. L.
Ma, Synth. Commun. 2005, 35, 2951; c) E. Rombi, I. Ferino, R.
Monaci, C. Picciau, V. Solinas, R. Buzzoni, Appl. Catal. A 2004, 266,
other coupling reactions.
[
[
26] J. Stetter, F. Lieb, Angew. Chem. 2000, 112, 1792; Angew. Chem. Int.
Ed. 2000, 39, 1724.
27] a) K. Isobe, S. Kawaguchi, Heterocycles 1981, 16, 1603; b) M. Beller,
W. Mägerlein, A. F. Indolese, C. Fischer,Synthesis 2001, 1098.
7
3; d) B. Lücke, K. V. Narayana, A. Martin, K. Jähnisch, Adv. Synth.
Catal. 2004, 346, 1407.
[
5] a) F. Hagedorn, H.-P. Gelbke in Ullmanns Encyklopädie der techni-
schen Chemie, Vol. 17 (Eds. E. BartholomØ, E. Biekert, H. Hell-
mann, H. Ley, W. M. Weigert, E. Weise), 4th ed., Verlag Chemie,
Received: January 18, 2007
Published online: May 7, 2007
6254
ꢁ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2007, 13, 6249 – 6254