Title: Regio- and Stereoselective Cyclization Reactions of Unsaturated Silyl Enol Ethers by Photoinduced Electron Transfer – Mechanistic Aspects and Synthetic Approach
Abstract: European Journal of Organic ChemistryVolume 1998, Issue 8 p. 1583-1596 Full Paper Regio- and Stereoselective Cyclization Reactions of Unsaturated Silyl Enol Ethers by Photoinduced Electron Transfer – Mechanistic Aspects and Synthetic Approach Sandra Hintz, Sandra Hintz Institut für Organische Chemie der Universität Kiel, Olshausenstrasse 40, D-24098 Kiel, Germany Fax: (internat.) + 49(0)431/880-7410Search for more papers by this authorJochen Mattay, Jochen Mattay [email protected] Search for more papers by this authorRudi van Eldik, Rudi van Eldik Institut für Anorganische Chemie der Universität Erlangen-Nürnberg, Egerlandstrasse 1, D-91058 Erlangen, GermanySearch for more papers by this authorWen-Fu Fu, Wen-Fu Fu Institut für Anorganische Chemie der Universität Erlangen-Nürnberg, Egerlandstrasse 1, D-91058 Erlangen, GermanySearch for more papers by this author Sandra Hintz, Sandra Hintz Institut für Organische Chemie der Universität Kiel, Olshausenstrasse 40, D-24098 Kiel, Germany Fax: (internat.) + 49(0)431/880-7410Search for more papers by this authorJochen Mattay, Jochen Mattay [email protected] Search for more papers by this authorRudi van Eldik, Rudi van Eldik Institut für Anorganische Chemie der Universität Erlangen-Nürnberg, Egerlandstrasse 1, D-91058 Erlangen, GermanySearch for more papers by this authorWen-Fu Fu, Wen-Fu Fu Institut für Anorganische Chemie der Universität Erlangen-Nürnberg, Egerlandstrasse 1, D-91058 Erlangen, GermanySearch for more papers by this author First published: August 1998 https://doi.org/10.1002/(SICI)1099-0690(199808)1998:8<1583::AID-EJOC1583>3.0.CO;2-RCitations: 32AboutPDF 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 Abstract Oxidative photoinduced electron transfer (PET) reactions have been performed with various silyl enol ethers and silyloxy-2H-chromones bearing an olefinic or silylacetylenic side chain. The reactions result in regioselective ring closure with the formation of bi- to tetracyclic ring systems with a well-defined ring juncture, e.g. perhydrophenanthrenones 13 or benzo-annellated xanthenones 24. Our investigations have focussed on the optimization of this cyclization method with regard to irradiation time and product yield. The irradiation times could be reduced by using the cosensitized PET method. Modifying the substrate at the silyl group led to enhanced yields. In addition, we found that solvent and pressure dependences are important tools, allowing control of the regiochemistry. Both the synthesis of 6-endo products by radical cationic reaction pathways, as well as 5-exo ring closure by radical intermediates was achieved. Mechanistic details, including findings from deuterium labelling experiments, are discussed. References 1 [1a] M. A. Fox, M. Chanon (Eds.), Photoinduced Electron Transfer, parts A–D, Elsevier, Amsterdam, 1988 –, Google Scholar[1b] J. Kavarnos, N. J. Turro, Chem. Rev. 1986, 86, 401–449. 10.1021/cr00072a005 CASWeb of Science®Google Scholar – [1c] J. Kavarnos, Fundamentals of Photoinduced Electron Transfer, VCH, Weinheim, 1993. Google Scholar – [1d] J. Mattay (Ed.), Top. Curr. Chem. 1990–1996, 156, 158, 159, 163, 177. Google Scholar – [1e] P. S. Mariano (Ed.), Advances in Electron Transfer Chemistry, JAI, Greenwich, 1991/1992, vols. 1–3. Google Scholar [1f] – J. Cossy, Bull. Soc. Chim. Fr. 1994, 131, 344–356. CASWeb of Science®Google Scholar 2 [2a] J. Mattay, M. Vondenhof, Top. Curr. Chem. 1991, 159, 219–255. 10.1007/3-540-53257-9_5 CASWeb of Science®Google Scholar [2b] – F. Müller, J. Mattay, Chem. Rev. 1993, 93, 99–117. 10.1021/cr00017a006 CASWeb of Science®Google Scholar 3 [3a] J. Mattay, Angew. Chem. 1987, 99, 849–870; 10.1002/ange.19870990906 CASGoogle Scholar Angew. Chem. Int. Ed. Engl. 1987, 26, 825. 10.1002/anie.198708251 Web of Science®Google Scholar [3b] – J. Mattay, Synthesis 1989, 233–252. 10.1055/s-1989-27214 CASGoogle Scholar 4 H. D. Roth, Top. Curr. Chem. 1992, 163, 131–245. 10.1007/3-540-55117-4_6 CASWeb of Science®Google Scholar 5 [5a] R. A. Neunteufel, D. R. Arnold, J. Am. Chem. Soc. 1973, 95, 4080–4081. 10.1021/ja00793a060 CASWeb of Science®Google Scholar [5b] – A. J. Maroulis, D. R. Arnold, Synthesis 1979, 819–820. 10.1055/s-1979-28846 Google Scholar [5c] – For a related oxidate addition see: E. Baciocchi, A. Casu, R. Ruzziconi, Synlett 1990, 679–680. 10.1055/s-1990-21209 Google Scholar 6 [6a] L. Eberson, Electron Transfer Reactions in Organic Chemistry, Springer, Berlin, 1987. 10.1007/978-3-642-72544-9 Google Scholar – [6b] J. K. Kochi in Comprehensive Organic Synthesis (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, vol. 7, pp 849–889. 10.1016/B978-0-08-052349-1.00216-X Google Scholar 7 [7a] S. Hintz, A. Heidbreder, J. Mattay, Top. Curr. Chem. 1996, 177, 77–124. 10.1007/3-540-60110-4_3 CASWeb of Science®Google Scholar [7b] – G. Pandey, Top. Curr. Chem. 1993, 168, 175–221. 10.1007/3-540-56746-1_11 CASWeb of Science®Google Scholar 8 [8a] B. B. Snider, T. Kwon, J. Org. Chem. 1990, 55, 4786–4788. 10.1021/jo00303a005 CASWeb of Science®Google Scholar [8b] – B. B. Snider, T. Kwon, J. Org. Chem. 1992, 57, 2399–2410. 10.1021/jo00034a038 CASWeb of Science®Google Scholar 9 [9a] K. D. Moeller, M. R. Marzabadi, D. G. New, M. Y. Chiang, S. Keith, J. Am. Chem. Soc. 1990, 112, 6123–6124. 10.1021/ja00172a035 CASWeb of Science®Google Scholar [9b] – K. D. Moeller, L. V. Tinao, J. Am. Chem. Soc. 1992, 114, 1033–1041. 10.1021/ja00029a036 CASWeb of Science®Google Scholar 10 [10a] S. Hintz, R. Fröhlich, J. Mattay, Tetrahedron Lett. 1996, 37, 7349–7352. 10.1016/0040-4039(96)01708-X CASWeb of Science®Google Scholar [10b] – S. Hintz, J. Mattay, J. Inf. Rec. 1996, 23, 35–38. CASWeb of Science®Google Scholar [10c] – A. Heidbreder, J. Mattay, J. Inf. Rec. 1994, 21, 575–577. CASGoogle Scholar [10d] – A. Heidbreder, J. Mattay, Tetrahedron Lett. 1992, 33, 1973–1976. 10.1016/0040-4039(92)88117-N CASWeb of Science®Google Scholar 11 [11a] E. Nakamura in Organocopper Reagents – A Practical Approach (Ed.: R. J. K. Taylor), IRL, Oxford, 1994, pp. 129–142. Google Scholar [11b] – S. Matsuzawa, Y. Horiguchi, E. Nakamura, I. Kuwajima, Tetrahedron 1989, 45, 349–362. 10.1016/0040-4020(89)80064-X CASWeb of Science®Google Scholar [11c] – Y. Horiguchi, S. Matsuzawa, E. Nakamura, I. Kuwajima, Tetrahedron Lett. 1986, 27, 4025–4028. 10.1016/S0040-4039(00)84901-1 CASWeb of Science®Google Scholar 12 [12a] P. Brownbridge, Synthesis 1983, 1–28. 10.1055/s-1983-30204 CASGoogle Scholar [12b] – J. K. Rasmussen, Synthesis 1977, 91–110. 10.1055/s-1977-24284 Web of Science®Google Scholar 13 H. Emde, D. Domsch, H. Feger, U. Frick, A. Götz, H. H. Hergott, K. Hofmann, W. Kober, K. Krägeloh, T. Oesterle, W. Steppan, W. West, G. Simchen, Synthesis 1982, 1–26. 10.1055/s-1982-29685 CASGoogle Scholar 14 S. Fukuzumi, M. Fujita, J. Otera, Y. Fujita, J. Am. Chem. Soc. 1992, 114, 10271–10278. 10.1021/ja00052a024 CASWeb of Science®Google Scholar 15 A. Weller, Z. Phys. Chem. (Munich) 1982, 133, 93–98. 10.1524/zpch.1982.133.1.093 CASWeb of Science®Google Scholar 16 [16a] B. B. Snider, C. P. Cartaya-Marin, J. Org. Chem. 1984, 49, 1688–1691. 10.1021/jo00184a003 CASWeb of Science®Google Scholar [16b] – D. L. Boger, R. J. Mathvink, J. Org. Chem. 1992, 57, 1429–1443. 10.1021/jo00031a021 CASWeb of Science®Google Scholar 17 [17a] H. O. House, G. H. Rasmusson, J. Org. Chem. 1963, 28, 31–34. 10.1021/jo01036a006 CASWeb of Science®Google Scholar [17b] – P. W. Concannon, J. Ciabattoni, J. Am. Chem. Soc. 1973, 95, 3284–3289. 10.1021/ja00791a035 CASWeb of Science®Google Scholar [17c] – C. D. Gutsche, H. H. Peter, J. Am. Chem. Soc. 1955, 77, 5971–5977. 10.1021/ja01627a054 CASWeb of Science®Google Scholar 18 A. L. J. Beckwith, C. H. Schiesser, Tetrahedron 1985, 41, 3925–3941. 10.1016/S0040-4020(01)97174-1 CASWeb of Science®Google Scholar 19 A. L. J. Beckwith, Tetrahedron 1981, 37, 3073–3100. 10.1016/S0040-4020(01)98839-8 CASWeb of Science®Google Scholar 20 [20a] K.-D. Krüger, X. Xing, M. Demuth, R. Goddard, M. Kessler, C. Krüger, Helv. Chim. Acta 1995, 78, 2065–2076. 10.1002/hlca.19950780815 CASWeb of Science®Google Scholar [20b] – K.-D. Warzecha, X. Xing, M. Demuth, Pure Appl. Chem. 1997, 69, 109–112. 10.1351/pac199769010109 CASWeb of Science®Google Scholar 21 [21a] T. V. Rajan Babu, Acc. Chem. Res. 1991, 24, 139–145. 10.1021/ar00005a003 CASWeb of Science®Google Scholar [21b] – D. P. Curran, D. M. Radiewicz, Tetrahedron 1985, 41, 3943–3958. 10.1016/S0040-4020(01)97175-3 CASWeb of Science®Google Scholar [21c] – C. P. Jasperse, D. P. Curran, T. L. Fevig, Chem. Rev. 1991, 91, 1237–1286. 10.1021/cr00006a006 CASWeb of Science®Google Scholar 22 M. Schmittel, M. Keller, A. Burghart, J. Chem. Soc., Perkin Trans. 2 1995, 2327–2333. Google Scholar 23 [23a] K. P. Dockery, J. P. Dinnocenzo, S. Farid, J. L. Goodman, I. R. Gould, W. P. Todd, J. Am. Chem. Soc. 1997, 119, 1876–1883. 10.1021/ja963197x CASWeb of Science®Google Scholar [23b] – J. P. Dinnocenzo, S. Farid, J. L. Goodman, I. R. Gould, W. P. Todd, J. Am. Chem. Soc. 1989, 111, 8973–8975. 10.1021/ja00206a061 CASWeb of Science®Google Scholar 24 C.-K. Sha, T.-S. Jean, D.-C. Wang, Tetrahedron Lett. 1990, 31, 3745–3748. 10.1016/S0040-4039(00)97460-4 CASWeb of Science®Google Scholar 25 A. Heidbreder, Ph. D. Thesis, Universität Münster, 1994. Google Scholar 26 Y. T. Jeon, C.-P. Lee, P. S. Mariano, J. Am. Chem. Soc. 1991, 113, 8863–8878. 10.1021/ja00023a038 CASWeb of Science®Google Scholar 27 [27a] R. van Eldik, T. Asano, W. J. le Noble, Chem. Rev. 1989, 89, 549–688. 10.1021/cr00093a005 CASWeb of Science®Google Scholar [27b] – F. G. Klärner, Chem. Unserer Zeit 1989, 2327–2333. Google Scholar – [27c] W. J. le Noble (Ed.), Organic High Pressure Chemistry, Elsevier, Amsterdam, 1988. Google Scholar – [27d] N. S. Isaacs, Liquid-Phase High-Pressure Chemistry, Wiley, New York, 1981. Google Scholar 28 [28a] M. K. Diedrich, D. Hochstrate, F.-G. Klärner, B. Zimny, Angew. Chem. 1994, 106, 1135–1137; 10.1002/ange.19941061008 CASGoogle Scholar Angew. Chem. Int. Ed. Engl. 1994, 33, 1079. 10.1002/anie.199410791 Web of Science®Google Scholar [28b] – F.-G. Klärner, B. Krawczyk, V. Ruster, U. K. Deiters, J. Am. Chem. Soc. 1994, 116, 7646–7657. 10.1021/ja00096a023 Web of Science®Google Scholar [28c] – W. von E. Doering, L. Birladeanu, K. Sarma, J. H. Teles, F.-G. Klärner, J.-S. Gehrke, J. Am. Chem. Soc. 1994, 116, 4289–4297. 10.1021/ja00089a018 CASWeb of Science®Google Scholar 29 W.-S. Chung, N. J. Turro, J. Mertes, J. Mattay, J. Org. Chem. 1989, 54, 4881–4887. 10.1021/jo00281a033 CASWeb of Science®Google Scholar 30 We are grateful to F.-G. Klärner (Essen) for helpful discussions and for pointing this alternative out to us. Meanwhile we have shown in an independent investigation of the PET-oxidative cyclization of 1-phenyl-1-trimethylsiloxy-1,6-heptadienes that acetonitrile favours the heterolytic cleavage of the silyl group under high pressure: L. Ackermann, A. Heidbreder, F.-G. Klärner, J. Mattay, F. Wurche, to be published. Google Scholar 31 MOLVOL calculations were performed by F.-G. Klärner (Essen). Google Scholar 32 E. F. Bradbrook, R. P. Linstead, J. Chem. Soc. 1936, 1739–1744. Google Scholar 33 P. Bercot, Bull. Soc. Chim. Fr. 1947, 304–307. Google Scholar 34 [34a] D. Magde, R. van Eldik in High-Pressure Techniques in Chemistry and Physics: A Practical Approach (Eds.: N. Isaacs, W. Holzapfel), Oxford University Press, Oxford, 1997, Chapter 6. Google Scholar [34b] – G. Stochel, R. van Eldik, Coord. Chem. Rev. 1997, 159, 153. 10.1016/S0010-8545(96)01295-7 CASWeb of Science®Google Scholar [34c] – W.-F. Fu, R. van Eldik, Organometallics 1997, 16, 572. 10.1021/om960531p CASWeb of Science®Google Scholar Citing Literature Volume1998, Issue8August 1998Pages 1583-1596 ReferencesRelatedInformation
Publication Year: 1998
Publication Date: 1998-08-01
Language: en
Type: article
Indexed In: ['crossref']
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Cited By Count: 38
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