Facile Formation of Chloro-η 3 -Allyl Complexes by Reaction of Vinyldiazoacetates and Ruthenium(II) Arene Complexes Hisao Nishiyama,* Miyuki Konno, and Katsuyuki Aoki School of Materials Science, Toyohashi University of Technology, Tempaku-cho, Toyohashi 441-8580, Japan Huw M. L. Davies Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260-3000 Received February 25, 2002 Summary: The reaction of vinyldiazoacetates 1 and ruthenium arene complexes 2 at room temperature resulted in the formation of a new type of chloro- substituted η 3 -allyl ruthenium complexes, 3, in high yield. The structure of 3a was determined by X-ray crystallographic analysis. The reaction of the ruthenium complexes 3a,d with styrene demonstrated that these complexes are capable of inducing a cyclopropanation reaction. Introduction The rhodium-catalyzed reactions of vinyldiazoacetates with olefins has been well-developed as a general method for the stereoselective synthesis of cyclopro- panes and cyclopentenes, and these reactions are be- lieved to proceed via metal carbenoids. 1,2 The Nishiyama group has investigated the carbenoid reactions and the carbene complexes derived from the reaction of various ruthenium species with diazoacetates and diazo- malonates. 3,4 In this paper, we disclose our studies on the reaction of several vinyldiazoacetates 1 with ruthe- nium arene complexes 2, which resulted in the unex- pected formation of novel η 3 -allyl ruthenium complexes 3. Results and Discussion Reaction of the vinyldiazoacetate 1a and the (η 6 - benzene)ruthenium complex 2a in dichloromethane at room temperature produced the new complex 3a (Scheme 1). The reaction was monitored by TLC, which showed the appearance of a new yellow spot. Purification by column chromatography gave a yellow solid, which on the basis of NMR analysis appeared to consist of two stereoisomers (ca. 94:6). X-ray crystallographic analysis of the main isomer demonstrated that it was not the anticipated ruthenium carbenoid complex. Instead, the quite unusual 1-chloro-substituted η 3 -allyl ruthenium complex 3a was formed with a Cl (syn) and CO 2 Me (anti) arrangement on the C1 carbon atom (Figure 1, Tables 1 and 2). 5 Probably, the minor product is the isomer with Cl (anti) and CO 2 Me (syn), but this cannot be fully characterized because the minor isomer was not isolated in pure form. When the (p-cymene)ruthenium (1) Davies, H. M. L. Curr. Org. Chem. 1998, 2, 463. Davies, H. M. L. Advances in Cycloaddition; Harmata, M., Ed.; JAI Press: New York, 1999; Vol. 5, p 119. Selected papers: Davies, H. M. L.; Bruzinski, P. R.; Lake, D. H.; Kong, N.; Fall, M. J. J. Am. Chem. Soc. 1996, 118, 6879. Davies, H. M. L.; Hansen, T. J. Am. Chem. Soc. 1997, 119, 9075. Davies, H. M. L.; Xiang, B.; Kong, N.; Stafford, D. G. J. Am. Chem. Soc. 2001, 123, 7461. (2) Doyle, M. P.; McKervey, M. A.; Ye, T. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds; Wiley: New York, 1998. Davies, H. M. L.; Antoulinakis, E. G. Organic Reactions; Overman, L. E., Ed.; Wiley: New York, 2001; Vol. 57, p 1. (3) Nishiyama, H.; Itoh, Y.; Matsumoto, H.; Park, S.-B.; Itoh, K. J. Am. Chem. Soc. 1994, 116, 2223. Nishiyama, H.; Itoh, Y.; Sugawara, Y.; Matsumoto, H.; Park, S.-B.; Itoh, K. Bull. Chem. Soc. Jpn. 1995, 68, 1247. Nishiyama, H.; Soeda, N.; Naito, T.; Motoyama, Y. Tetrahe- dron: Asymmetry 1998, 9, 2865. Iwasa, S.; Takezawa, F.; Tuchiya, Y.; Nishiyama, H. Chem. Commun. 2001, 59. For vinylcarbene complexes of Ru, for example: Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1995, 117, 5503. Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100. Nishiyama, H.; Park, S.-B.; Itoh, K. Chem. Lett. 1995, 599 and references therein. (4) For (arene)ruthenium complex catalyzed cyclopropanations; see for example: Ku ¨ cu ¨ kbay, H.; Cetinkaya, B.; Guesmi, S.; Dixneuf, P. H. Organometallics 1996, 15, 2434. Simal, F.; Jan, D.; Demonceau, A.; Noels, A. F. Tetrahedron Lett. 1999, 40, 1653. Baratta, W.; Herrmann, W. A.; Kratzer, R. M.; Rigo, R. Organometallics 2000, 19, 3664. (5) Maxwell, J. L.; Brown, K. C.; Bartley, D. W.; Kodadek, T. Science 1992, 256, 1544. An intermediate carbene species of the rhodium- porphyrin system was captured by iodine anion to form iodomethyl species in the absence of styrene. Scheme 1 2536 Organometallics 2002, 21, 2536-2539 10.1021/om020160e CCC: $22.00 © 2002 American Chemical Society Publication on Web 05/16/2002