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Fluorous 4‐ N , N ‐Dimethylaminopyridine (DMAP) Salts as Simple Recyclable Acylation Catalysts

2010; Wiley; Volume: 16; Issue: 6 Linguagem: Inglês

10.1002/chem.200902982

ISSN

1521-3765

Autores

Daniela Vuluga, Julien Legros, Benoı̂t Crousse, Danièle Bonnet‐Delpon,

Tópico(s)

Synthesis and Catalytic Reactions

Resumo

Chemistry – A European JournalVolume 16, Issue 6 p. 1776-1779 Communication Fluorous 4-N,N-Dimethylaminopyridine (DMAP) Salts as Simple Recyclable Acylation Catalysts Daniela Vuluga, Daniela Vuluga BioCIS-CNRS, Faculté de Pharmacie-Paris Sud, 5 rue Jean-Baptiste Clément, F-92296 Châtenay-Malabry (France), Fax: (+33) 146-83-57-40Search for more papers by this authorJulien Legros Dr., Julien Legros Dr. [email protected] BioCIS-CNRS, Faculté de Pharmacie-Paris Sud, 5 rue Jean-Baptiste Clément, F-92296 Châtenay-Malabry (France), Fax: (+33) 146-83-57-40Search for more papers by this authorBenoit Crousse Dr., Benoit Crousse Dr. BioCIS-CNRS, Faculté de Pharmacie-Paris Sud, 5 rue Jean-Baptiste Clément, F-92296 Châtenay-Malabry (France), Fax: (+33) 146-83-57-40Search for more papers by this authorDanièle Bonnet-Delpon Dr., Danièle Bonnet-Delpon Dr. BioCIS-CNRS, Faculté de Pharmacie-Paris Sud, 5 rue Jean-Baptiste Clément, F-92296 Châtenay-Malabry (France), Fax: (+33) 146-83-57-40Search for more papers by this author Daniela Vuluga, Daniela Vuluga BioCIS-CNRS, Faculté de Pharmacie-Paris Sud, 5 rue Jean-Baptiste Clément, F-92296 Châtenay-Malabry (France), Fax: (+33) 146-83-57-40Search for more papers by this authorJulien Legros Dr., Julien Legros Dr. [email protected] BioCIS-CNRS, Faculté de Pharmacie-Paris Sud, 5 rue Jean-Baptiste Clément, F-92296 Châtenay-Malabry (France), Fax: (+33) 146-83-57-40Search for more papers by this authorBenoit Crousse Dr., Benoit Crousse Dr. BioCIS-CNRS, Faculté de Pharmacie-Paris Sud, 5 rue Jean-Baptiste Clément, F-92296 Châtenay-Malabry (France), Fax: (+33) 146-83-57-40Search for more papers by this authorDanièle Bonnet-Delpon Dr., Danièle Bonnet-Delpon Dr. BioCIS-CNRS, Faculté de Pharmacie-Paris Sud, 5 rue Jean-Baptiste Clément, F-92296 Châtenay-Malabry (France), Fax: (+33) 146-83-57-40Search for more papers by this author First published: 28 January 2010 https://doi.org/10.1002/chem.200902982Citations: 41Read 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 Pass the salt please! A simple fluorous salt of 4-N,N-dimethylaminopyridine (C7F15CO2H⋅DMAP) that acts as an effective recyclable organocatalyst for esterification under solvent- and base-free conditions is reported. This catalyst is readily accessible, easy to handle and to recover, and constitutes an attractive alternative for cleaner and safer acylation reactions (see scheme). 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 chem_200902982_sm_miscellaneous_information.pdf7.7 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 1Special issue on "Recoverable Catalysts and Reagents" Ed.: J. A. Gladysz Chem. Rev. 2002, 102, 3215. 2For reviews on supported organocatalysts, see: 2aF. Cozzi, Adv. Synth. Catal. 2006, 348, 1367; 2bM. Benaglia, A. Puglisi, F. Cozzi, Chem. Rev. 2003, 103, 3401. 3 3aL. M. Litvinenko, A. I. Kirichenko, Dokl. Akad. Nauk SSSR 1967, 176, 97; 3bW. Steglich, G. Höfle, Angew. Chem. 1969, 81, 1001; Angew. Chem. Int. Ed. Engl. 1969, 8, 981. 4For a review, see: R. P. Wurz, Chem. Rev. 2007, 107, 5570. 5 5aI. Held, E. Larionov, C. Bozler, F. Wagner, H. Zipse, Synthesis 2009, 2267; 5bS. Singh, G. Das, O. V. Singh, H. Han, Org. Lett. 2007, 9, 401; 5cS. Singh, G. Das, O. V. Singh, H. Han, Tetrahedron Lett. 2007, 48, 1983; 5dI. Held, S. Xu, H. Zipse, Synthesis 2007, 1185; 5eM. R. Heinrich, H. S. Klisa, H. Mayr, W. Steglich, H. Zipse, Angew. Chem. 2003, 115, 4975; Angew. Chem. Int. 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Zhang, Chem. Rev. 2004, 104, 2531; 13dHandbook of Fluorous Chemistry, (Eds.: J. A. Gladysz, D. P. Curran, I. T. Horváth), Wiley-VCH, Weinheim, 2004. 14For pioneering work, see: I. T. Horváth, J. Rábai, Science 1994, 266, 72. 15For a review, see: W. Zhang, D. P. Curran, Tetrahedron 2006, 62, 11837. 16 16aM. Wende, R. Meier, J. A. Gladysz, J. Am. Chem. Soc. 2001, 123, 11490; 16bM. Wende, J. A. Gladysz, J. Am. Chem. Soc. 2003, 125, 5861. 17Teflon tape has also been used for fluorous catalyst delivery/recovery, see: L. V. Dinh, J. A. Gladysz, Angew. Chem. 2005, 117, 4164; Angew. Chem. Int. Ed. 2005, 44, 4095. 18For fluorous TEMPO, see: 18aA. Gheorghe, T. Chinnusamy, E. Cuevas-Yañez, P. Hilgers, O. Reiser, Org. Lett. 2008, 10, 4171; for fluorous (S)-pyrrolidine sulfonamide, see: 18bL. Zu, H. Xie, H. Li, J. Wang, W. Wang, Org. Lett. 2008, 10, 1211; 18cL. Zu, J. Wang, H. Li, W. Wang, Org. Lett. 2006, 8, 3077; for fluorous 4-dialkylaminopyridine, see: 18dJ. Legros, B. Crousse, D. Bonnet-Delpon, J. Fluorine Chem. 2008, 129, 974 in the Special Issue "Dennis P. Curran ACS Award for Creative Work in Fluorine Chemistry" (Eds.: G. K. Surya Prakash, W. R. Dolbier, Jr.); for fluorous chiral imidazolidinone, see: 18eQ. Chu, W. Zhang, D. P. Curran, Tetrahedron Lett. 2006, 47, 9287; for fluorous Corey–Bakshi–Shibata (CBS) reagent, see: 18fZ. Dalicsek, F. Pollreisz, A. Gömöry, T. Soós, Org. Lett. 2005, 7, 3243; for fluorous cinchona alkaloids, see: 18gF. Fache, O. Piva, Tetrahedron Lett. 2001, 42, 5655. 19For a remarkable effect of the fluorine atom in proline catalysis, see: C. Sparr, W. B. Schweizer, H. M. Senn, R. Gilmour, Angew. Chem. 2009, 121, 3111; Angew. Chem. Int. Ed. 2009, 48, 3065. 20S. Xu, I. Held, B. Kempf, H. Mayr, W. Steglich, H. Zipse, Chem. Eur. J. 2005, 11, 4751. 21A. Sakakura, K. Kawajiri, T. Ohkubo, Y. Kosugi, K. Ishihara, J. Am. Chem. Soc. 2007, 129, 14775. 22K.-U. Goss, Environ. Sci. Technol. 2008, 42, 456–458; additions and corrections: K.-U. Goss, Environ. Sci. Technol. 2008, 42, 5032. 23In an NMR tube, AcOH (1 equiv) was added to a solution of DMAP in CDCl3: a downfield shift of the proton in position 2 from δ=6.47 ppm to δ=6.53 ppm was observed, characteristic of AcOH⋅DMAP. A further equivalent of C7F15CO2H was then added, which provoked a further shift to δ=6.72 ppm, matching with the NMR spectroscopy data of pure C7F15CO2H⋅DMAP 1-Rf15 (δ=6.71 ppm) (see the Supporting Information for details). 24With 1-Rf15, total conversion of the alcohol to the ester occurred in less than 17 h, whereas the reaction was still incomplete after 30 h in the presence of C7F15CO2H as a catalyst. 25Note that C7F15CO2H and 1-Rf15 slowly solubilize in the reaction medium, whereas 1-Rf23 is only sparingly soluble. According to the report by Ishihara and co-workers (ref. [21]), it can be assumed that the low solubility of 1-Rf23 disfavors the release of free DMAP, thus, explaining the moderate activity in the acetylation reaction (58 % conversion after 8 h). Citing Literature Volume16, Issue6February 8, 2010Pages 1776-1779 ReferencesRelatedInformation

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