ORGANIC
LETTERS
2003
Vol. 5, No. 3
317-320
Iron-Mediated Electrochemical Reaction
of r-Chloroesters with Carbonyl
Compounds
Muriel Durandetti,* Clothilde Meignein, and Jacques Pe´richon
Laboratoire d'Electrochimie, Catalyse et Synthe`se Organique, CNRS, UMR 7582,
UniVersite´ Paris 12, 2 rue Henri-Dunant, 94320 Thiais, France
durandetti@glVt-cnrs.fr
Received November 19, 2002
ABSTRACT
Reformatsky-type reactions have been performed efficiently using an electroassisted iron-complex catalysis. Valuable product such as
â-hydroxyesters, ketones or nitriles are thus prepared with high yields.
The reaction of an R-haloester with an aldehyde or a ketone
in the presence of zinc metal to give a â-hydroxy-ester,1 the
Reformatsky reaction, is a well-recognized carbon-carbon
bond-forming reaction2 (Scheme 1).
etc. More recently, sonoelectroreduction of zinc powder has
given a highly reactive zinc, which reacts with R-bromoesters
or allylic compounds.7 Another process has been performed,
in aqueous THF, using BF3OEt2 and Zn dust but is limited
to aldehydes.8 Recently, a Reformatsky-type reaction was
developed, using RhCl(PPh3)3 and diethylzinc.9 Besides the
classical zinc method, various other metals have been
examined so far, such as chromium,10 indium,11 manganese,12
etc. In our laboratory, we have already described some
electrochemical processes for the Reformatsky reaction.13
More recently, we have reported an electrochemical method,
catalytic in both chromium and nickel salts, using a sacrificial
stainless steel or iron rod anode.14 In these conditions,
â-hydroxyesters are obtained in good yields (60-80%) and
Scheme 1. Reformatsky Reaction.
To extend the scope of this reaction, various parameters
have been extensively investigated. Since the reaction is
initiated by insertion of zinc into the halogen-carbon bond,
most efforts have been focused on the activation of zinc such
as Rieke-Zn,3 Zn-Cu couple,4 Zn/Ag-graphite,5 ultrasound,6
(7) Durant, A.; Delplanche, J.; Libert, V.; Reisse, J. Eur. J. Org. Chem.
1999, 2845-2852.
(8) Chattopadhyay, A.; Salaskar, A. Synthesis 2000, 561-564.
(9) Kanai, K.; Wakabayashi, H.; Honda, T. Org. Lett. 2000, 2, 2549-
2551.
(1) Reformatsky, S. Chem. Ber. 1887, 20, 1210.
(2) For recent reviews of the Reformatsky reaction, see: (a) Fu¨rstner,
A. Synthesis 1989, 571-590. (b) Rathke, M. W.; Weipert, P. In Compre-
hensiVe Organic Synthesis; Trost, B. M., I. Fleming, I., Eds.; Pergamon:
New York, 1991; Vol. 2, pp 277-299. (c) Fu¨rstner, A. In Organozinc
Reagents; Knochel, P., Jones, P., Eds.; Oxford University Press: New York,
1999; pp 287-305.
(10) Wessjohann, L.; Gabriel, T. J. Org. Chem. 1997, 62, 3772-3774.
(11) (a) Hirashita, T.; Kinoshita, K.; Yamamura, H.; Kawai, M.; Araki,
S. J. Chem. Soc., Perkin Trans. 1 2000, 5, 825-828. (b) Lee, P.; Bang, K.;
Sung, S.; Chang, S. Synth. Commun. 2001, 31, 3781-3789.
(12) (a) Kahiga, H.; Nishimae, S.; Shinokubo, H.; Oshima, K. Tetra-
hedron 2001, 57, 8807-8815. (b) Cahiez, G.; Chavant, P.-Y. Tetrahedron
Lett. 1989, 30, 7373-7376.
(3) Rieke, R. D.; Uhm, S. J. Synthesis 1975, 452.
(13) (a) Rollin, Y.; Gebehenne, C.; Derien, S.; Dunach, E.; Pe´richon, J.;
J. Orgonomet. Chem. 1993, 461, 9-14. (b) Connan, A.; Sibille, S.; Pe´richon,
J. J. Org. Chem. 1991, 56, 2018-2024.
(4) Santaniello, E.; Manzocchi, A. Synthesis 1977, 698.
(5) Csuk, R.; Fu¨rster, A.; Weidmann, H. J. Chem. Soc., Chem. Commun.
1986, 775.
(14) Durandetti, M.; Ne´delec, J.-Y.; Pe´richon, J. Org. Lett. 2001, 3,
2073.
(6) Han, B.; Boudjouk, P. J. Org. Chem. 1982, 47, 5030.
10.1021/ol0273046 CCC: $25.00 © 2003 American Chemical Society
Published on Web 01/11/2003