S. Bellemin-Laponnaz et al.
FULL PAPER
[6]
gata, M. A. Zamora, S. Zacchino, C. P. Sosa, R. D. Enriz, I. G.
Csizmadia, THEOCHEM 1999, 463, 271.
P. Milko, J. Roithova, D. Schröder, J. Lemaire, H. Schwarz,
M. C. Holthausen, Chem. Eur. J. 2008, 14, 4318.
T.-H. Chan, A. Melnyk, J. Am. Chem. Soc. 1970, 92, 3718.
J.-X. Chen, J. F. Daeuble, D. M. Brestensky, J. M. Stryker, Tet-
rahedron 2000, 56, 2153.
a) M. R. Churchill, S. A. Bezman, J. A. Osborn, J. Wormald,
Inorg. Chem. 1972, 11, 1818; b) T. H. Lemmen, K. Folting, J. C.
Huffman, K. G. Caulton, J. Am. Chem. Soc. 1985, 107, 7774.
G. V. Goeden, J. C. Huffman, K. G. Caulton, Inorg. Chem.
1986, 25, 2484.
N. P. Mankad, D. S. Laitar, J. P. Sadighi, Organometallics 2004,
23, 3369–3371.
NHC ligands offer low kinetic lability with transition metals.
Thus, several copper(I) species have been fully characterized by
coordination of NHC ligands to the metal center. See ref.[32]
and for example: a) L. A. Goj, E. D. Blue, C. Munro-Leighton,
T. B. Gunnoe, J. L. Petersen, Inorg. Chem. 2005, 44, 8647–8649;
b) L. A. Goj, E. D. Blue, S. A. Delp, T. B. Gunnoe, T. R. Cund-
ari, A. W. Pierpont, J. L. Petersen, P. D. Boyle, Inorg. Chem.
2006, 45, 9032–9045; c) K. X. Bhattacharyya, J. A. Akana,
D. S. Laitar, J. M. Berlin, J. P. Sadighi, Organometallics 2008,
27, 2682–2684; NHC ligands have allowed complete characteri-
zation of monomeric gold(I) hydride complexes, see: d) E. Y.
Tsui, P. Müller, J. P. Sadighi, Angew. Chem. Int. Ed. 2008, 47,
8937–8940.
a) G. Zhu, M. Terry, X. Zhang, J. Organomet. Chem. 1997,
547, 97; b) Y. Nishibayashi, I. Takei, S. Uemura, M. Hidai,
Organometallics 1998, 17, 3420; c) C. Moreau, C. G. Frost, B.
Murrer, Tetrahedron Lett. 1999, 40, 5617.
a) H. Mimoun, J. Y. de Saint Laumer, L. Giannini, R. Scopel-
liti, C. Floriani, J. Am. Chem. Soc. 1999, 121, 6158; b) V. Bette,
A. Mortreux, D. Savoia, J.-F. Carpentier, Tetrahedron 2004, 60,
2837; c) V. Bette, A. Mortreux, D. Savoia, J.-F. Carpentier, Adv.
Synth. Catal. 2005, 347, 289.
J. Yun, S. L. Buchwald, J. Am. Chem. Soc. 1999, 121, 5640.
a) B. K. Langlotz, H. Wadepohl, L. H. Gade, Angew. Chem.
Int. Ed. 2008, 47, 4670; b) N. S. Shaikh, S. Enthaler, K. Junge,
M. Beller, Angew. Chem. Int. Ed. 2008, 47, 2497.
For reviews on hydrosilylation of ketones, see: a) J.-F. Carpent-
ier, V. Bette, Curr. Org. Chem. 2002, 6, 913; b) O. Riant, N.
Mostefaï, J. Courmacel, Synthesis 2004, 2943; c) C. Deutsch,
N. Krause, B. H. Lipshutz, Chem. Rev. 2008, 108, 2916; d) S.
Díez-González, S. P. Nolan, Acc. Chem. Res. 2008, 41, 349.
H. Brunner, W. Miehling, J. Organomet. Chem. 1984, 275,
C17.1.
[27]
[7]
[28]
[29]
[30]
[8]
[9]
[31]
[32]
[33]
[10]
[11]
[12]
[13]
B. H. Lipshutz, K. Noson, W. Chrisman, J. Am. Chem. Soc.
2001, 123, 12917.
For other examples of copper-based systems for asymmetric
hydrosilylation of ketones, see: a) S. Sirol, J. Courmacel, N.
Mostefaï, O. Riant, Org. Lett. 2001, 3, 4111; b) J. Courmacel,
N. Mostefaï, S. Sirol, S. Chopin, O. Riant, Isr. J. Chem. 2002,
41, 231; c) D.-w. Lee, J. Yun, Tetrahedron Lett. 2004, 45, 5415;
d) J. Wu, J.-X. Ji, A. S. C. Chan, Proc. Natl. Acad. Sci. USA
2005, 102, 3570; e) M. L. Kantam, S. Laha, J. Yadav, P. R.
Likhar, B. Sreedhar, B. M. Choudary, Adv. Synth. Catal. 2007,
349, 1797; f) N. Mostefaï, S. Sirol, J. Courmacel, O. Riant,
Synthesis 2007, 8, 1265; g) M. L. Kantam, S. Laha, J. Yadav,
P. R. Likhar, B. Sreedhar, S. Jha, S. Bhargava, M. Udayakiran,
B. Jagadeesh, Org. Lett. 2008, 10, 2979.
a) D. H. Appella, Y. Moritani, R. Shintani, E. M. Ferreira,
S. L. Buchwald, J. Am. Chem. Soc. 1999, 121, 9473; b) Y. Mori-
tani, D. H. Appela, V. Jurkauskas, S. L. Buchwald, J. Am.
Chem. Soc. 2000, 122, 6797.
B. H. Lipshutz, K. Noson, W. Chrisman, A. Lower, J. Am.
Chem. Soc. 2003, 125, 8779.
[34]
[35]
G. V. Goeden, K. G. Caulton, J. Am. Chem. Soc. 1981, 103,
7354.
Stryker and collaborators also suggested that the active species
in the ketone reduction with [(Ph3P)CuH]6 is probably at a
lower aggregate (possibly monomeric), see: a) W. S. Mahoney,
J. M. Stryker, J. Am. Chem. Soc. 1989, 111, 8818; b) J.-X. Chen,
J. F. Daeuble, D. M. Brestensky, J. M. Stryker, Tetrahedron
2000, 56, 2153.
T. Satyanarayana, S. Abraham, H. B. Kagan, Angew. Chem.
Int. Ed. 2009, 48, 456.
CuCl/NaOt-Bu/BINAP as catalytic system (5 mol-%), aceto-
phenone as substrate, PhMeSiH2 as silane: see data in Support-
ing Information
[14]
[36]
[37]
[15]
[16]
[17]
[18]
J. T. Issenhuth, S. Dagorne, S. Bellemin-Laponnaz, Adv. Synth.
Catal. 2006, 348, 1991.
[38]
[39]
M. Kitamura, S. Suga, H. Oka, R. Noyori, J. Am. Chem. Soc.
1998, 120, 9800.
H. Ito, T. Ishizuka, T. Okumura, H. Yamanaka, J. Tateiwa, M.
Sonoda, A. Hosomi, J. Organomet. Chem. 1999, 574, 102.
Two different diphosphane ligands were used in this study:
2,2Ј-bis(diphenylphosphanyl)-1,1Ј-binaphthyl (BINAP) and
2,2-dimethyl-1,3-bis(diphenylphosphanyl)propane (DMDP).
F. P. Notter, Ph. D. Thesis, Université de Strasbourg, 2008.
a) H. Tamura, H. Yamasaki, H. Sato, S. Sakaki, J. Am. Chem.
Soc. 2003, 125, 16114; b) S. Sakaki, T. Takayama, M. Sumim-
oto, M. Sugimoto, J. Am. Chem. Soc. 2004, 126, 3332; c) M.
Sumimoto, N. Iwane, T. Takahama, S. Sakaki, J. Am. Chem.
Soc. 2004, 126, 10457; d) B. O. Leung, D. L. Reid, D. A. Arm-
strong, A. Rauk, J. Phys. Chem. A 2004, 108, 2720; e) A. A. C.
Braga, G. Ujaque, F. Maseras, Organometallics 2006, 25, 3647;
f) P. Deglmann, E. Ember, P. Hofmann, S. Pitter, O. Walter,
Chem. Eur. J. 2007, 13, 2864.
S. C. A. H. Pierrefixe, F. M. Bickelhaupt, Struct. Chem. 2007,
18, 813.
R. Hoffmann, J. M. Howell, E. L. Muetterties, J. Am. Chem.
Soc. 1972, 94, 3047.
S. C. A. Y. Pierrefixe, C. F. Guerra, F. M. Bickelhaupt, Chem.
Eur. J. 2008, 14, 819.
Goldfuss and collaborators observed a linear relationship be-
tween the ee of product and that of ligand in the case of dialk-
ylzinc additions to benzaldehyde using chiral anisyl fenchols.
Ab initio calculations of homo- and heterochiral dimers re-
vealed energy differences up to 3.0 kcalmol–1, see: M. Steigel-
mann, Y. Nisar, F. Rominger, B. Goldfuss, Chem. Eur. J. 2002,
8, 5211.
We are well aware however that the DFT calculations may not
take properly into account weak interactions such as π-π inter-
actions or CH/π interactions. Thus the agreement between
theory and experiment may be regarded as fortuitous. Yet the
overall consistency of the experimental and theoretical results
adds credence to our final conclusions.
Note that Osakada et al. studied the stability of copper alk-
oxide (Ph3P)3Cu-OCHPh2 and found that decomposition by
thermolysis (at 200 °C for 20 min) of the complex could lead
to a mixture of benzophenone and diphenylmethanol, see: K.
Osakada, T. Takizawa, M. Tanaka, T. Yamamoto, J. Or-
ganomet. Chem. 1994, 473, 359.
A catalytic cycle that contains an enantioselectivity determin-
ing step different from the rate limiting step was also postulated
for the titanium-catalyzed hydrosilylation of ketones. The hy-
pothesis was proposed based on the rate enhancement when
alcohol was added to the reaction mixture. Such a positive
alcohol effect was also observed in some cases with copper hy-
dride-catalyzed reactions, see references 8 and 10c.
[19]
[20]
[40]
[41]
[42]
[21]
[22]
[23]
[24]
[25]
[26]
M. Onda, Y. Kohama, K. Suga, I. Yamaguchi, J. Mol. Struct.
1998, 442, 19.
G. De Luca, M. Longeri, G. Pileio, P. Lantto, ChemPhysChem
2005, 6, 2086.
a) T. Miyahara, T. Inazu, THEOCHEM 1996, 364, 131; b)
A. N. Rodriguez, F. A. Giannini, H. A. Baldoni, L. N. Santa-
540
www.eurjic.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 529–541