Title: Palladium‐Catalyzed Diastereo‐ and Enantioselective Synthesis of Substituted Cyclopentanes through a Dynamic Kinetic Asymmetric Formal [3+2]‐Cycloaddition of Vinyl Cyclopropanes and Alkylidene Azlactones
Abstract: Angewandte Chemie International EditionVolume 50, Issue 27 p. 6167-6170 Communication Palladium-Catalyzed Diastereo- and Enantioselective Synthesis of Substituted Cyclopentanes through a Dynamic Kinetic Asymmetric Formal [3+2]-Cycloaddition of Vinyl Cyclopropanes and Alkylidene Azlactones† Prof. Barry M. Trost, Corresponding Author Prof. Barry M. Trost [email protected] Department of Chemistry, Stanford University, 337 Campus Drive, Stanford CA 94305 (USA)Department of Chemistry, Stanford University, 337 Campus Drive, Stanford CA 94305 (USA)Search for more papers by this authorPatrick J. Morris, Patrick J. Morris Department of Chemistry, Stanford University, 337 Campus Drive, Stanford CA 94305 (USA)Search for more papers by this author Prof. Barry M. Trost, Corresponding Author Prof. Barry M. Trost [email protected] Department of Chemistry, Stanford University, 337 Campus Drive, Stanford CA 94305 (USA)Department of Chemistry, Stanford University, 337 Campus Drive, Stanford CA 94305 (USA)Search for more papers by this authorPatrick J. Morris, Patrick J. Morris Department of Chemistry, Stanford University, 337 Campus Drive, Stanford CA 94305 (USA)Search for more papers by this author First published: 23 May 2011 https://doi.org/10.1002/anie.201101684Citations: 201 † This work has been supported by the National Science Foundation and the National Institutes of Health (GM033049). The authors thank Johnson Matthey for the gift of palladium salts, Dr. Allen Oliver of Notre Dame for X-ray crystallography, and Dr. Kami Hull for editorial assistance. Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract An enantioselective preparation of vinylcyclopentanes has been achieved through the title reaction (see scheme). A range of aryl, heterocyclic, alkenyl, and alkyl substituted azlactone alkylidenes have been utilized, giving the cyclopentane products in good yield, diastereomeric ratio, and enantioselectivity. Supporting Information Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Filename Description anie_201101684_sm_miscellaneous_information.pdf786.7 KB miscellaneous_information Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. References 1 1aM. Lautens, W. Klute, W. Tam, Chem. Rev. 1996, 96, 49–92; 1bT. Hudlicky, J. D. Price, Chem. Rev. 1989, 89, 1467–1486; 1cC. E. Masse, J. S. Panek, Chem. Rev. 1995, 95, 1293–1316; 1dG. Helmchen, M. Ernst, G. Paradies, Pure Appl. Chem. 2004, 76, 495–506; 1eR. D. Little in Comprehensive Organic Synthesis, Vol. 5 (Eds.: ), Pergamon, New York, 1991, pp. 239–270. 2For recent examples utilizing allenoates as a three-carbon fragment, see 2aH. Xiao, Z. Chai, C. Zheng, Y. Yang, W. Liu, J. Zhang, G. Zhao, Angew. Chem. 2010, 122, 4569–4572; Angew. Chem. Int. Ed. 2010, 49, 4467–4470; 2bJ. E. Wilson, G. C. Fu, Angew. Chem. 2006, 118, 1454–1457; Angew. Chem. Int. Ed. 2006, 45, 1426–1429; 2cB. J. Cowen, S. J. Miller, J. Am. Chem. Soc. 2007, 129, 10988–10989; for recent examples utilizing trimethylenemethane as a three-carbon fragment, see 2dB. M. Trost, N. Cramer, S. M. Silverman, J. Am. Chem. Soc. 2007, 129, 11236–11237; 2eB. M. Trost, J. P. Stambuli, S. M. Silverman, U. Schworer, J. Am. Chem. Soc. 2006, 128, 13328–13329; also see 2fH. M. L. Davies, B. Ciang, N. Kong, D. G. Stafford, J. Am. Chem. Soc. 2001, 123, 7461–7462. 3I. Shimizu, Y. Ohashi, J. Tsuji, Tetrahedron Lett. 1985, 26, 3825–3828. 4I. Shimizu, Y. Ohashi, J. Tsuji, Chem. Lett. 1987, 6, 1157–1158. 5B. M. Trost, D. R. Fandrick, J. Am. Chem. Soc. 2003, 125, 11836–11837. 6C. Larksarp, H. Alper, J. Org. Chem. 1998, 63, 6229–6233. 7A. T. Parsons, M. J. Campbell, J. S. Johnson, Org. Lett. 2008, 10, 2541–2544. 8A. T. Parsons, J. S. Johnson, J. Am. Chem. Soc. 2009, 131, 3122–3123. 9A. T. Parsons, A. G. Smith, A. J. Neel, J. S. Johnson, J. Am. Chem. Soc. 2010, 132, 9688–9692. 10B. M. Trost, D. Van Vranken, Angew. Chem. 1992, 104, 194–196; Angew. Chem. Int. Ed. Engl. 1992, 31, 228–230; 10bB. M. Trost, M. R. Machacek, A. Aponick, Acc. Chem. Res. 2006, 39, 747–760; 10cC. P. Butts, E. Filali, G. C. Lloyd-Jones, P. Norrby, D. A. Sale, Y. Schramm, J. Am. Chem. Soc. 2009, 131, 9945–9957. 11 11aN. Arumugam, J. Jayashankaran, R. Manian, R. Raghunathan, Tetrahedron 2005, 61, 8512–8516; 11bA. Avenoza, J. H. Busto, C. Cativiela, J. M. Peregrina, Tetrahedron 1994, 50, 12989–12998. 12The change in pKa of the corresponding malonate switches from 16 to 11 in DMSO, see 12aW. N. Olmstead, F. W. Bordwell, J. Org. Chem. 1980, 45, 3299–3305; 12bJ. M. Takacs, Z. Xu, X. Jiang, A. Leonovl, G. Theriot, Org. Lett. 2002, 4, 3843–3845; 12cM. Mishima, M. Matsuoka, Y. X. Lei, A. Rappoport, J. Org. Chem. 2004, 69, 5947–5965. 13B. M. Trost, F. D. Toste, J. Am. Chem. Soc. 1999, 121, 4545–4554. 14The relative and absolute configurations of the other products are assigned by analogy to 5 b. 15The heats of formation of 5 b and epi-5 b were calculated using SPARTAN 06 Essential 1.0.1. Epi-5 b was found to be 11.6 kJ mol−1 more stable. For details, see Supporting Information. 16CCDC 825686 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Citing Literature Volume50, Issue27June 27, 2011Pages 6167-6170 ReferencesRelatedInformation