Ruthenium Pincer-Catalyzed Acylation of Alcohols Using Esters
Experimental Section
[3] For recent contributions regarding catalytic transesteri-
fication, see: a) M. I. de Sairre, E. S. Bronze-Uhle,
P. M. Donate, Tetrahedron Lett. 2005, 46, 2705; b) P.
Jiang, D. Zhang, Q. Li, Y. Lu, Catal. Lett. 2006, 110,
General Procedure for the Catalytic Acylation of
Alcohols
1
01; c) N. Remme, K. Koschek, C. Schneider, Synlett
Complex 1 (0.05 mmol), ester (5 mmol), alcohol (15 mmol)
and toluene (3 mL) were added to a Schlenk flask under an
atmosphere of nitrogen in a Vacuum Atmospheres glove-
box. The flask was equipped with a condenser and the solu-
tion was refluxed with stirring in an open system under
argon for the specified time (Table 1). In the case of isopro-
pyl alcohol, the reactions were performed in a closed system
at 1358C. The reaction products were analyzed by GC-MS.
After cooling to room temperature, m-xylene (1 mmol) or
benzene (1 mmol) was added as internal standard to the re-
action mixture and the products were quantitatively ana-
lyzed by GC using a Carboxen 1000 column on an HP 690
series GC system or HP-5 cross linked 5% PH ME Siloxane
column (30 mꢁ0.32 mmꢁ0.25 mm film thickness) on an HP
2007, 491, 493; d) G. C. M. Kondaiah, L. A. Reddy,
K. S. Babu, V. M. Gurav, K. G. Huge, R. Bandichhor,
P. P. Reddy, A. Bhattacharya, R. V. Anand, Tetrahedron
Lett. 2008, 49, 106; e) T. Ohshima, T. Iwasaki, Y. Mae-
gawa, A. Yoshiyama, K. Mashima, J. Am. Chem. Soc.
2
008, 130, 2944; f) N. Inahashi, T. Fujiwara, T. Sato,
Synlett 2008, 605; g) B. Martꢂn-Matute, M. Edin, K.
Bogꢃr, J-E. Bꢄckvall, Angew. Chem. 2004, 116, 6697;
Angew. Chem. Int. Ed. 2004, 43, 6535; h) T. Zeng, G.
Song, C-J. Li, Chem. Commun. 2009, 6249; i) K. Ishi-
hara, M. Niwa, Y. Kosugi, Org. Lett. 2008, 10, 2187;
j) S. Magens, M. Ertelt, A. Jatsch, B. Plietker, Org.
Lett. 2008, 10, 53; k) M-H. Lin, T. V. Rajanbabu, Org.
Lett. 2000, 2, 997; l) T. Iwasaki, Y. Maegawa, Y. Haya-
shi, T. Ohshima, K. Mashima, Synlett 2009, 1659;
m) G. A. Grasa, R. M. Kissling, S. P. Nolan, Org. Lett.
6890 series GC system. In the reaction of cyclohexanol and
esters, evaporation of the solvent, followed by purification
over basic alumina column chromatography afforded the
2
002, 4, 3583; n) G. W. Nyce, J. A. Lamboy, E. Connor,
R. M. Waymouth, J. L. Hedrick, Org. Lett. 2002, 4,
587; o) G. A. Grasa, T. Guveli, R. Singh, S. P. Nolan, J.
1
pure transesters. H NMR spectra of the products isolated
from the catalytic reactions were as reported in the litera-
ture. The characterization data are available in the Support-
ing Information.
3
Org. Chem. 2003, 68, 2812.
[
4] J. Zhang, G. Leitus, Y. Ben-David, D. Milstein, J. Am.
Chem. Soc. 2005, 127, 10840.
[
5] a) J. Zhang, M. Gandelman, L. J. W. Shimon, D. Mil-
stein, Dalton Trans. 2007, 107; b) J. Zhang, M. Gandel-
man, L. J. W. Shimon, D. Milstein, Organometallics
Acknowledgements
2
004, 23, 4026; c) C. Gunanathan, L. J. W. Shimon, D.
This research was supported by the European Research
Council under the FP7 framework (ERC No 246837), by the
Israel Science Foundation, and by the Helen and Martin
Kimmel Center for Molecular Design. D. M is the Israel
Matz Professorial Chair of Organic Chemistry.
Milstein, J. Am. Chem. Soc. 2009, 131, 3146.
6] J. Zhang, G. Leitus, Y. Ben-David, D. Milstein, Angew.
Chem. 2006, 118, 1131; Angew. Chem. Int. Ed. 2006, 45,
1113.
[
[
7] a) C. Gunanathan, Y. Ben-David, D. Milstein, Science
2
007, 317, 790; b) B. Gnanaprakasam, J. Zhang, D. Mil-
stein, Angew. Chem. 2010, 122, 1510; Angew. Chem.
Int. Ed. 2010, 49, 1468.
References
[
8] a) E. Ben Ari, G. Leitus, L. J. W. Shimon, D. Milstein J.
Am. Chem. Soc. 2006, 128, 15390; b) M. Iron, E. Ben-
Ari, R. Cohen, D. Milstein Dalton Trans. 2009, 9433;
c) E. Khaskin, M. A. Iron, L. J. W. Shimon, J. Zhang,
D. Milstein J. Am. Chem. Soc. 2010, 132, 8542; d) S. W.
Kohl, L. Weiner, L. Schwartsburd, L. Konstantinovski,
L. J. W. Shimon, Y. Ben-David, M. A. Iron, D. Milstein,
Science 2009, 324, 74.
[
1] a) Comprehensive Organic Synthesis, (Eds.: B. M. Trost,
I. Fleming), Pergamon Press, New York, 1992; b) R. C.
Larock, in: Comprehensive Organic Transformations,
2
nd edn., Wiley-VCH, New York, 1996; c) J. Otera, in:
Esterification Methods, Reactions and Applications,
Wiley-VCH, Weinheim, 2003.
[
2] For reviews on transesterifications, see: a) J. Otera,
Chem. Rev. 1993, 93, 1449; b) J. Otera, Esterification,
Wiley-VCH Verlag GmbH, Weinheim, Germany, 2003;
c) J. Otera, Acc. Chem. Res. 2004, 37, 288; d) G. A.
Grasa, R. Singh, S. P. Nolan, Synthesis 2004, 971, 985;
e) H. E. Hoydonckx, D. E. De Vos, S. A. Chavan, P. A.
Jacobs, Top. Catal. 2004, 27, 83; f) D. Enders, O. Nieme-
ier, A. Henseler, Chem. Rev. 2007, 107, 5606.
[9] All of the ethyl acetate has disappeared; due to its vol-
atility, some ethyl acetate might have been lost during
reflux.
[10] Excess cyclohexanol remained mostly unreacted under
the reaction conditions, with a small amount of cyclo-
hexanone being formed.
Adv. Synth. Catal. 2010, 352, 3169 – 3173
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3173