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Intermolecular Addition of Glycosyl Halides to Alkenes Mediated by Visible Light

2010; Wiley; Volume: 49; Issue: 40 Linguagem: Inglês

10.1002/anie.201004311

1521-3773

Robert S. Andrews, Jennifer J. Becker, Michel R. Gagné,

Catalytic C–H Functionalization Methods

Angewandte Chemie International EditionVolume 49, Issue 40 p. 7274-7276 Communication Intermolecular Addition of Glycosyl Halides to Alkenes Mediated by Visible Light† R. Stephen Andrews, R. Stephen Andrews Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3290 (USA)Search for more papers by this authorDr. Jennifer J. Becker, Dr. Jennifer J. Becker US Army Research Office, P.O. Box 12211, Research Triangle Park, NC 27709 (USA)Search for more papers by this authorProf. Dr. Michel R. Gagné, Prof. Dr. Michel R. Gagné [email protected] Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3290 (USA)Search for more papers by this author R. Stephen Andrews, R. Stephen Andrews Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3290 (USA)Search for more papers by this authorDr. Jennifer J. Becker, Dr. Jennifer J. Becker US Army Research Office, P.O. Box 12211, Research Triangle Park, NC 27709 (USA)Search for more papers by this authorProf. Dr. Michel R. Gagné, Prof. Dr. Michel R. Gagné [email protected] Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3290 (USA)Search for more papers by this author First published: 25 August 2010 https://doi.org/10.1002/anie.201004311Citations: 246 † We thank Aaron J. Francis for his contribution to optimization and Prof. Malcolm Forbes for his help with EPR experiments. The Army Research Office Staff Research Funding and Department of Energy (DE-FG02-05ER15630) are gratefully acknowledged for their support. 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 Catching photons: Visible light, an amine reductant, and a [Ru(bpy)3]2+ photocatalyst can be used to mediate the addition of glycosyl halides into alkenes to synthesize important C-glycosides (see scheme). This method shows the growing potential of photocatalysis to effectively drive useful and difficult chemical transformations. 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_201004311_sm_miscellaneous_information.pdf778.9 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 1For recent reviews in C-glycoside biology, see: 1aC. H. Lin, H. C. Lin, W. B. Yang, Curr. Top. Med. Chem. 2005, 5, 1431–1457; 1bP. G. Hultin, Curr. Top. Med. Chem. 2005, 5, 1299–1331; 1cW. Zou, Curr. Top. Med. Chem. 2005, 5, 1363–1391; 1dP. Compain, O. R. Martin, Bioorg. Med. Chem. 2001, 9, 3077–3092; 1eF. Nicotra, Top. Curr. Chem. 1997, 187, 55–83. 2aP. Meo, H. M. I. 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Somsak, Tetrahedron Lett. 2007, 48, 7351–7353; 5cS. K. Readman, S. P. Marsden, A. Hodgson, Synlett 2000, 1628–1630; 5dH. Gong, R. Sinisi, M. R. Gagné, J. Am. Chem. Soc. 2007, 129, 1908–1909; 5eH. Gong, M. R. Gagné, J. Am. Chem. Soc. 2008, 130, 12177–12183. 6S. Yamago, H. Miyazoe, J. Yoshida, Tetrahedron Lett. 1999, 40, 2339–2342. 7H. Gong, R. S. Andrews, J. L. Zuccarello, S. J. Lee, M. R. Gagné, Org. Lett. 2009, 11, 879–882. 8For recent reviews on [Ru(bpy)3]2+ catalysis with visible light, see: K. Zeitler, Angew. Chem. 2009, 121, 9969–9974; Angew. Chem. Int. Ed. 2009, 48, 9785–9789; J. M. R. Narayanam, C. R. J. Stephenson, Chem. Soc. Rev. DOI: ; T. P. Yoon, M. A. Ischay, J. Du, Nat. Chem. 2010, 2, 527–532. This methodology has been used for enantioselective α alkylation of aldehydes; see: D. A. Nicewicz, D. W. C. MacMillan, Science 2008, 322, 77–80; D. A. Nagib, M. E. Scott, D. W. C. MacMillan, J. Am. Chem. Soc. 2009, 131, 10875–10877. For [2+2] cycloadditions, see: M. A. Ischay, M. E. Anzovino, J. Du, T. P. Yoon, J. Am. Chem. Soc. 2008, 130, 12886–12887; J. Du, T. P. Yoon, J. Am. Chem. Soc. 2009, 131, 14604–14605; M. A. Ischay, X. Lu, T. P. Yoon, J. Am. Chem. Soc. 2010, 132, 8572–8574. For reductive dehalogenation, see: J. M. R. Narayanam, J. W. Tucker, C. R. J. Stephenson, J. Am. Chem. Soc. 2009, 131, 8756–8757. For intramolecular addition into alkenes, see: J. W. Tucker, J. M. R. Narayanam, S. W. Krabbe, C. R. J. Stephenson, Org. Lett. 2010, 12, 368–371; J. W. Tucker, J. D. Nguyen, J. M. R. Narayanam, S. W. Krabbe, C. R. J. Stephenson, Chem. Commun. 2010, 46, 4985–4987. For intermolecular addition into arenes, see: L. Furst, B. S. Matsuura, J. M. R. Narayanam, J. W. Tucker, C. R. J. Stephenson, Org. Lett. 2010, 12, 3104–3107. 9 9aJ. Dupuis, B. Giese, D. Rüegge, H. Fishcer, H. G. Korth, R. Sustmann, Angew. Chem. 1984, 96, 887–888; Angew. Chem. Int. Ed. Engl. 1984, 23, 896–898; 9bH. G. Korth, R. Sustmann, J. Dupuis, B. Giese, J. Chem. Soc. Perkin Trans. 2 1986, 1453–1459; 9cY. Araki, T. Endo, M. Tanji, J. Nagasawa, Tetrahedron Lett. 1987, 28, 5853–5856. 10The reduction potential of glucosyl bromide tetraacetate has been measured to be −1.27 V (versus SCE). See: S. B. Rondinini, P. R. Mussini, F. Crippa, G. Sello, Electrochem. Commun. 2000, 2, 491–496. 11Salt electrolytes were also added, but they were less effective than acid additive. 12 12aB. Giese, Rev. Chem. Intermed. 1986, 7, 3; 12bB. Giese, Angew. Chem. 1983, 95, 771–782; Angew. Chem. Int. Ed. Engl. 1983, 22, 753–764. 13The major competing byproduct was reductive debromination of the starting material. Hydrolysis of the glucosyl bromide was also observed in small amounts (<20 %). 14Alkenes that are more electron-rich than methyl acrylate were unreactive (acrylamide, ethyl vinyl ether) and led to slow reductive debromination of the starting material. 15With M. Forbes (UNC-CH); full details will be provided in a future publication. See the Supporting Information for a typical scan. 16 16aJ.-P. Cheng, Y. Lu, X.-Q. Zhu, Y. Sun, F. Bi, J. He, J. Org. Chem. 2000, 65, 3853–3857; 16bX.-Q. Zhu, H.-R. Li, Q. Li, T. Ai, J.-Y. Lu, Y. Yang, J.-P. Cheng, Chem. Eur. J. 2003, 9, 871–880; 16cX.-Q. Zhu, L. Cao, Y. Liu, Y. Yang, J.-Y. Lu, J.-S. Wang, J.-P. Cheng, Chem. Eur. J. 2003, 9, 3937–3945. 17[4,4-D2]5 was shown to provide 3 only partially deuterated in the α position (20–25 %), suggesting that multiple pathways for α reduction were operating (Scheme 2, box). Citing Literature Volume49, Issue40September 24, 2010Pages 7274-7276 ReferencesRelatedInformation