N-Heterocyclic Carbene Piano-Stool Iron Complexes as Efficient Catalysts for Hydrosilylation
vacuum three cycles) distilled toluene (2.5 mL) was added
followed by aldehyde (0.5 mmol) and PhSiH3 (62 mL,
0.5 mmol). The reaction mixture was stirred in a preheated
oil bath at 308C for 3 h.
Procedure B: A 10-mL oven-dried Schlenk tube contain-
ing a stirring bar, was charged with [CpFe(CO)2ACTHUNTGRENNG(U IMes)]I 1
Chem. Int. Ed. 2008, 47, 3317–3321; d) A. Correa, O.
Garcia Mancheno, C. Bolm, Chem. Soc. Rev. 2008, 37,
1108–1117; e) B. D. Sherry, A. Fꢆrstner, Acc. Chem.
Res. 2008, 41, 1500–1511; f) W. M. Czaplik, M. Mayer,
J. Cvengros, A. Jacobi von Wangelin, ChemSusChem
2009, 2, 396–417.
(3.0 mg, 0.005 mmol). After purging with argon (argon-
vacuum three cycles) distilled THF (2.5 mL) was added fol-
lowed by aldehyde (0.5 mmol) and PhSiH3 (62 mL,
0.5 mmol). The reaction mixture was stirred in a preheated
oil bath at 708C for 1 h under the presence of visible light.
For both procedures, 1 mL of MeOH and 1 mL of 2M
NaOH solution were then successively added under vigo-
rous stirring for 1 hour at room temperature. Conversion
[6] a) J. Louie, R. H. Grubbs, Chem. Commun. 2000,
1479–1480; b) D. S. McGuinness, V. C. Gibson, J. W.
Steed, Organometallics 2004, 23, 6288–6292; c) M.-Z.
Chen, H.-M. Sun, W.-F. Li, Z.-G. Wang, Q. Shen, Y.
Zhang, J. Organomet. Chem. 2006, 691, 2489–2494.
[7] G. Hilt, P. Bolze, I. Kieltsch, Chem. Commun. 2005,
1996–1998.
[8] a) N. Saino, D. Kogure, S. Okamoto, Org. Lett. 2005, 7,
3065–3067; b) N. Saino, D. Kogure, K. Kase, S. Okamo-
to, J. Organomet. Chem. 2006, 691, 3129–3136.
[9] a) R. B. Bedford, M. Betham, D. W. Bruce, A. A. Da-
nopoulos, R. M. Frost, M. Hird, J. Org. Chem. 2006, 71,
1104–1110; b) T. Hatakeyama, M. Nakamura, J. Am.
Chem. Soc. 2007, 129, 9844–9845; c) T. Hatakeyama, S.
Hashimoto, K. Ishizuka, M. Nakamura, J. Am. Chem.
Soc. 2009, 131, 11949–11963; d) T. Yamagami, R. Shin-
tani, E. Shirakawa, T. Hayashi, Org. Lett. 2007, 9,
1045–1048.
1
was determined by H NMR. The reaction mixture was ex-
tracted with diethyl ether (2ꢄ10 mL). The combined organic
layers were washed with brine (3ꢄ10 mL), dried over anhy-
drous MgSO4, filtered and concentrated under vacuum. The
residue was purified by silica gel column chromatography
using ethyl acetate-petroleum ether mixture (10 to 50%) to
afford the desired product.
Acknowledgements
[10] B. Plietker, A. Dieskau, K. Mçws, A. Jatsch, Angew.
Chem. 2008, 120, 204–207; Angew. Chem. Int. Ed.
2008, 47, 198–201.
We are grateful to Universitꢀ de Rennes 1, CNRS, Rennes
Mꢀtropole and Ministꢁre de l’Enseignement Supꢀrieur et de
la Recherche for support, the latter for a PhD grant to D.B.,
and the European Union through network IDECAT.
[11] J. N. Rosa, R. S. Reddy, N. R. Candeias, P. M. S. D. Cal,
P. M. P. Gois, Org. Lett. 2010, 12, 2686–2690.
[12] For some representative examples, see: a) A. A. Dano-
poulos, J. A. Wright, W. B. Motherwell, Chem.
Commun. 2005, 784–786; b) D. Pugh, N. J. Wells, D. J.
Evans, A. A. Danopoulos, Dalton Trans. 2009, 7189–
7195; c) Y. S. Wang, H. M. Sun, X. P. Tao, Q. Shen, Y.
Zhang, Chin. Sci. Bull. 2007, 52, 3193–3199.
References
[1] A. J. Arduengo, R. L. Harlow, M. Kline, J. Am. Chem.
Soc. 1991, 113, 361–363.
[2] a) K. ꢁfele, J. Organomet. Chem. 1968, 12, 42–43;
b) H.-W. Wanzlick, H.-J. Schçnherr, Angew. Chem.
1968, 80, 154–154; Angew. Chem. Int. Ed. Engl. 1968,
7, 141–142.
[13] P. Buchgraber, L. Toupet, V. Guerchais, Organometal-
lics 2003, 22, 5144–5147.
[14] a) L. Mercs, G. Labat, A. Neels, A. Ehlers, M. Al-
brecht, Organometallics 2006, 25, 5648–5656; b) L.
Mercs, A. Neels, H. Stoeckli-Evans, M. Albrecht,
Dalton Trans. 2009, 7168–7178; c) L. Mercs, A. Neels,
M. Albrecht, Dalton Trans. 2008, 5570–5576.
[3] For some representative examples, see: a) B. Cetin-
kaya, P. Dixneuf, M. F. Lappert, J. Chem. Soc. Chem.
Commun. 1973, 206–206; b) B. Cetinkaya, P. Dixneuf,
M. F. Lappert, J. Chem. Soc. Dalton Trans. 1974, 1827–
1833; c) M. F. Lappert, J. Organomet. Chem. 2005, 690,
5467–5473.
[4] Some representative reviews: a) S. Diꢀz-Gonzalez, N.
Marion, S. P. Nolan, Chem. Rev. 2009, 109, 3612–3676;
b) O. Schuster, L. Yang, H. G. Raubenheimer, M. Al-
brecht, Chem. Rev. 2009, 109, 3445–3478; c) R. Cor-
berꢅn, E. Mas-Marzꢅ, E. Peris, Eur. J. Inorg. Chem.
2009, 1700–1716; d) F. E. Hahn, Angew. Chem. 2006,
118, 1374–1378; Angew. Chem. Int. Ed. 2006, 45, 1348–
1352; e) W. A. Herrmann, Angew. Chem. 2002, 114,
1342–1363; Angew. Chem. Int. Ed. 2002, 41, 1290–
1309.
[15] S. A. Llewellyn, M. L. H. Green, J. C. Green, A. R.
Cowley, Dalton Trans. 2006, 2535–2541.
[16] V. Cꢀsar, N. Lugan, G. Lavigne, J. Am. Chem. Soc.
2008, 130, 11286–11287.
[17] a) Y. Ohli, T. Hatanaka, K. Tatsumi, J. Am. Chem. Soc.
2008, 130, 17174–17186; b) T. Hatanaka, Y. Ohki , K.
Tatsumi, Chem. Asian J. 2010, 5, 1657–1666.
[18] During the course of our investigation, E. Peris has re-
ported the synthesis and the application for the hydro-
silylation of electrodeficient aldehydes of tethered Cp-
NHC iron complexes, see: V. V. K. M. Kandepi, J. M. S.
Cardoso, E. Peris, B. Royo, Organometallics 2010, 29,
2777–2782.
[19] a) X.-F. Wu, C. Darcel, Eur. J. Org. Chem. 2009, 1144–
1147; b) X.-F. Wu, D. Bezier, C. Darcel, Adv. Synth.
Catal. 2009, 351, 367–370; c) X.-F. Wu, C. Vovard-Le
Bray, L. Bechki, C. Darcel, Tetrahedron 2009, 65,
7380–7384; d) X.-F. Wu, C. Darcel, Eur. J. Org. Chem.
2009, 4753–4765.
[5] For representative reviews of the state of the art, see:
a) C. Bolm, J. Legros, J. Le Paih, L. Zani, Chem. Rev.
2004, 104, 6217–6254; b) B. Plietker, in: Iron Catalysis
in Organic Chemistry, (Ed.: B. Plietker), Wiley-VCH
Verlag, Weinheim, 2008; c) S. Enthaler, K. Junge, M.
Beller, Angew. Chem. 2008, 120, 3363–3367; Angew.
Adv. Synth. Catal. 2011, 353, 239 – 244
ꢃ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
243