H. Terai, Angew. Chem., Int. Ed., 2005, 44, 6931;
(c) S.-I. Murahashi, T. Nakae, H. Terai and N. Komiya, J. Am.
Chem. Soc., 2008, 130, 11005.
Notes and references
1 (a) E. J. Corey and X.-M. Cheng, The Logic of Chemical Synthesis,
Wiley, New York, 1989; (b) J. Fuhrhop and G. Penzlin, Organic
Synthesis, VCH, Weinheim, 2nd edn, 1994.
2 (a) M. Tobisu and N. Chatani, Angew. Chem., Int. Ed., 2006, 45,
1683; (b) F. Kakiuchi and N. Chatani, Adv. Synth. Catal., 2003,
345, 1077.
3 (a) C.-J. Li, Acc. Chem. Res., 2009, 42, 335; (b) C. I. Herrerias,
X. Yao, Z. Li and C.-J. Li, Chem. Rev., 2007, 107, 2546;
(c) K. R. Campos, Chem. Soc. Rev., 2007, 36, 1069; (d) Z. Li,
D. S. Bohle and C.-J. Li, Proc. Natl. Acad. Sci. U. S. A., 2006, 103,
8928.
13 S. Singhal, S. L. Jain and B. Sain, Chem. Commun., 2009, 2371.
14 (a) W. Nam, Acc. Chem. Res., 2007, 40, 522; (b) I. G. Denisov,
T. M. Makris, S. G. Sligar and I. Schlichting, Chem. Rev., 2005,
105, 2253; (c) E. Y. Tshuva and S. J. Lippard, Chem. Rev., 2004,
104, 987; (d) M. Costas, M. P. Mehn, M. P. Jensen and L. Que Jr.,
Chem. Rev., 2004, 104, 939; (e) P. R. Ortiz de Montellano and
J. J. de Voss, Nat. Prod. Rep., 2002, 19, 477.
15 J. Iley and R. Tolando, J. Chem. Soc., Perkin Trans. 2, 2000, 2328.
16 S. Murata, K. Teramoto, M. Miura and M. Nomura, Bull. Chem.
Soc. Jpn., 1993, 66, 1297.
4 S.-I. Murahashi and D. Zhang, Chem. Soc. Rev., 2008, 37, 1490.
5 Reviews on iron catalysis in organic synthesis: (a) A. Furstner,
17 Solvolyses of a-aminonitriles in the presence of cupric or ferrous
ions have been reported. These reactions were rationalized by
assuming that these metal ions remove cyanide ions from the
aminonitrile–iminium cyanide equilibrium by precipitating insoluble
¨
Angew. Chem., Int. Ed., 2009, 48, 1364; (b) B. D. Sherry and
A. Furstner, Acc. Chem. Res., 2008, 41, 1500; (c) Iron Catalysis in
¨
Organic Chemistry, ed. B. Plietker, Wiley-VCH, Weinheim, 2008;
(d) A. Correa, O. Garcia Mancheno and C. Bolm, Chem. Soc. Rev.,
2008, 37, 1108; (e) E. B. Bauer, Curr. Org. Chem., 2008, 12, 1341;
(f) S. Enthaler, K. Junge and M. Beller, Angew. Chem., Int. Ed.,
2008, 47, 3317; (g) C. Bolm, J. Legros, J. Le Paih and L. Zani,
Chem. Rev., 2004, 104, 6217.
salts: (a) G. Buchi and H. Wuest, J. Org. Chem., 1974, 96, 7573;
(b) K. Takahashi, T. Mikajiri, H. Kurita, K. Ogura and H. Iida,
J. Org. Chem., 1985, 50, 4372.
¨
¨
18 Under similar conditions the use of other solvents was less efficient
(isolated yields of 2): tert-butanol (47%), ethanol (53%), aceto-
nitrile (52%), 2,2,2-trifluoroethanol (71%), isopropanol (78%).
19 Reducing the excess of TMSCN (1.5 equiv.) required extended
reaction times (24 h, 85% yield), and the use of equimolar amounts
of TMSCN affected the yield of 2 (24 h, 69%).
6 C(sp3)–H activation in benzylic positions: (a) Z. Li, L. Cao and
C.-J. Li, Angew. Chem., Int. Ed., 2007, 46, 6505; (b) Y.-Z. Li,
B.-J. Li, X.-Y. Lu, S. Lin and Z.-J. Shi, Angew. Chem., Int. Ed.,
2009, 48, 3817.
20 The presence of additional n-Bu4N1CNꢀ (1.0 equiv.) under
otherwise optimized reaction conditions (cf. entry 8 of Table 1)
7 C(sp3)–H activation adjacent to heteroatoms: Z. Li, R. Yu and
H. Li, Angew. Chem., Int. Ed., 2008, 47, 7497.
8 C(sp3)–H activation adjacent to nitrogen: C. M. Rao Volla and
P. Vogel, Org. Lett., 2009, 11, 1701.
resulted in
a slight retardation of the cyanation reaction
(63% isolated yield of 2 after 12 h) possibly because of a decrease
in the concentration of the active catalyst.
9 C(sp3)–H activation in hydrocarbons: Y. Zhang and C.-J. Li, Eur.
J. Org. Chem., 2007, 4654.
21 S. Murata, M. Miura and M. Nomura, J. Chem. Soc., Chem.
Commun., 1989, 116.
10 (a) Yu. M. Shafran, V. A. Bakulev and V. S. Mokrushin, Russ.
Chem. Rev., 1989, 58, 148 (Usp. Khim., 1989, 58, 250);
(b) D. Enders and J. P. Shilvock, Chem. Soc. Rev., 2000, 29, 359.
11 (a) M. North, Angew. Chem., Int. Ed., 2004, 43, 4126;
(b) A. Schmidt, in Science of Synthesis, ed. S.-I. Murahashi,
Thieme, Stuttgart, 2004, vol. 19, ch. 19.5.3, pp. 133–161.
12 (a) S.-I. Murahashi, N. Komiya, H. Terai and T. Nakae, J. Am.
Chem. Soc., 2003, 125, 15312; (b) S.-I. Murahashi, N. Komiya and
22 The oxidative a-cyanation of 2-phenyl-1,2,3,4-tetrahydro-isoquinoline
(36% yield) with CuBr (5 mol%)/TBHP/malononitrile at room
temperature has been described: Z. Li and C.-J. Li, Eur. J. Org.
Chem., 2005, 3173.
23 C(sp3)–H bond activation adjacent to nitrogen in aliphatic tertiary
amines with CuBr/NBS: M. Niu, Z. Yin, H. Fu, Y. Jiang and
Y. Zhao, J. Org. Chem., 2008, 73, 3961.
ꢂc
This journal is The Royal Society of Chemistry 2009
5026 | Chem. Commun., 2009, 5024–5026