Demetalation of Metal Porphyrins via Magnesium Porphyrins by Reaction with Grignard Reagents
2013; Wiley; Volume: 19; Issue: 28 Linguagem: Inglês
10.1002/chem.201301146
ISSN1521-3765
AutoresKei Murakami, Yutaro Yamamoto, Hideki Yorimitsu, Atsuhiro Osuka,
Tópico(s)Porphyrin Metabolism and Disorders
ResumoChemistry – A European JournalVolume 19, Issue 28 p. 9123-9126 Communication Demetalation of Metal Porphyrins via Magnesium Porphyrins by Reaction with Grignard Reagents Dr. Kei Murakami, Dr. Kei Murakami Department of Chemistry, Graduate School of Science, Kyoto University Kitashirakawa, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970Search for more papers by this authorYutaro Yamamoto, Yutaro Yamamoto Department of Chemistry, Graduate School of Science, Kyoto University Kitashirakawa, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970Search for more papers by this authorProf. Dr. Hideki Yorimitsu, Corresponding Author Prof. Dr. Hideki Yorimitsu [email protected] Department of Chemistry, Graduate School of Science, Kyoto University Kitashirakawa, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970 ACT-C (Japan) Science and Technology Agency (Japan)Department of Chemistry, Graduate School of Science, Kyoto University Kitashirakawa, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970Search for more papers by this authorProf. Dr. Atsuhiro Osuka, Corresponding Author Prof. Dr. Atsuhiro Osuka [email protected] Department of Chemistry, Graduate School of Science, Kyoto University Kitashirakawa, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970Department of Chemistry, Graduate School of Science, Kyoto University Kitashirakawa, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970Search for more papers by this author Dr. Kei Murakami, Dr. Kei Murakami Department of Chemistry, Graduate School of Science, Kyoto University Kitashirakawa, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970Search for more papers by this authorYutaro Yamamoto, Yutaro Yamamoto Department of Chemistry, Graduate School of Science, Kyoto University Kitashirakawa, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970Search for more papers by this authorProf. Dr. Hideki Yorimitsu, Corresponding Author Prof. Dr. Hideki Yorimitsu [email protected] Department of Chemistry, Graduate School of Science, Kyoto University Kitashirakawa, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970 ACT-C (Japan) Science and Technology Agency (Japan)Department of Chemistry, Graduate School of Science, Kyoto University Kitashirakawa, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970Search for more papers by this authorProf. Dr. Atsuhiro Osuka, Corresponding Author Prof. Dr. Atsuhiro Osuka [email protected] Department of Chemistry, Graduate School of Science, Kyoto University Kitashirakawa, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970Department of Chemistry, Graduate School of Science, Kyoto University Kitashirakawa, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970Search for more papers by this author First published: 05 June 2013 https://doi.org/10.1002/chem.201301146Citations: 29Read 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 Novel transformations of metal porphyrins, such as nickel, zinc, copper, and silver porphyrins, to magnesium porphyrins are described. The reactions were accomplished by using 4-methylphenylmagnesium bromide in toluene. The scope of the reactions was wide and various magnesium porphyrins were obtained (see figure). The products, acid-sensitive magnesium porphyrins, were smoothly converted to free-base porphyrins under weakly acidic conditions. Supporting Information As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Filename Description chem_201301146_sm_miscellaneous_information.pdf1.2 MB 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 1a Handbook of Porphyrin Science, Vols. 1–10 (Eds: ), World Scientific Publishing, Singapore, 2010; 1b Handbook of Porphyrin Science, Vols. 11–15 (Eds: ), World Scientific Publishing, Singapore, 2011; 1c Handbook of Porphyrin Science, Vols. 16–25 (Eds: ), World Scientific Publishing, Singapore, 2012; 1d The Porphyrin Handbook, Vols. 1–10 (Eds: ), Academic Press, San Diego, 2000; 1e Handbook of Porphyrin Science, Vols. 11–20 (Eds: ), Academic Press, San Diego, 2003; 1fD. Dolphin, The Porphyrins, Vols. 1 and 2, Academic Press, New York, 1979. 2 2aM. O. Senge, Chem. Commun. 2011, 47, 1943; 2bS. Horn, K. Dahms, M. O. Senge, J. 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Senge, Tetrahedron Lett. 2009, 50, 2566. 14Zinc porphyrin 1 Zn was much more reactive and less nucleophilic phenylmagnesium bromide could be employed to afford 1 Mg in 95 % yield. 15Reductive demetalation of silver and copper porphyrins by NaBH4 has been reported, while examples were limited to octaethylporphyrin and its derivatives: 15aJ. P. Collman, C. S. Bencosme, R. R. Durand, Jr., R. P. Kreh, F. C. Anson, J. Am. Chem. Soc. 1983, 105, 2699; 15bJ. A. Cowan, J. K. M. Sanders, Tetrahedron Lett. 1986, 27, 1201. 16Single electron transfer from the Grignard reagent is also a possible pathway as proposed in ref. [7]. 17 17aW. Kaschube, K. R. Pörschke, K. Angermund, C. Krüger, G. Wilke, Chem. Ber. 1988, 121, 1921; 17bJ. Terao, M. Tomita, S. P. Singh, N. Kambe, Angew. Chem. 2010, 122, 148; Angew. Chem. Int. Ed. 2010, 49, 144. Citing Literature Volume19, Issue28July 8, 2013Pages 9123-9126 ReferencesRelatedInformation
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