Nucleophilic Silylenoid Character of Stable Phosphonium Sila–ylides

Chemistry – A European JournalVolume 16, Issue 28 p. 8255-8258 Communication Nucleophilic Silylenoid Character of Stable Phosphonium Sila–ylides David Gau, David Gau Université de Toulouse, UPS, LHFA, 118 route de Narbonne, 31062 Toulouse, France, and CNRS, LHFA UMR 5069, 31062 Toulouse (France), Fax: (+33) 5-6155-8204Search for more papers by this authorRicardo Rodriguez Dr., Ricardo Rodriguez Dr. Université de Toulouse, UPS, LHFA, 118 route de Narbonne, 31062 Toulouse, France, and CNRS, LHFA UMR 5069, 31062 Toulouse (France), Fax: (+33) 5-6155-8204Search for more papers by this authorTsuyoshi Kato Dr., Tsuyoshi Kato Dr. [email protected] Université de Toulouse, UPS, LHFA, 118 route de Narbonne, 31062 Toulouse, France, and CNRS, LHFA UMR 5069, 31062 Toulouse (France), Fax: (+33) 5-6155-8204Search for more papers by this authorNathalie Saffon-Merceron Dr., Nathalie Saffon-Merceron Dr. Université de Toulouse, UPS, Structure Fédérative Toulousaine en Chimie Moléculaire, SFTCM FR2599, 118 route de Narbonne, 31062 Toulouse (France)Search for more papers by this authorFernando P. Cossío Prof., Fernando P. Cossío Prof. Departamento de Química Orgínica I, Universidad del País Vasco-Euskal Herriko Unibertsitatea Facultad de Química, P. K. 1072, San Sebastian–Donostia (Spain)Search for more papers by this authorAntoine Baceiredo Dr., Antoine Baceiredo Dr. Université de Toulouse, UPS, LHFA, 118 route de Narbonne, 31062 Toulouse, France, and CNRS, LHFA UMR 5069, 31062 Toulouse (France), Fax: (+33) 5-6155-8204Search for more papers by this author David Gau, David Gau Université de Toulouse, UPS, LHFA, 118 route de Narbonne, 31062 Toulouse, France, and CNRS, LHFA UMR 5069, 31062 Toulouse (France), Fax: (+33) 5-6155-8204Search for more papers by this authorRicardo Rodriguez Dr., Ricardo Rodriguez Dr. Université de Toulouse, UPS, LHFA, 118 route de Narbonne, 31062 Toulouse, France, and CNRS, LHFA UMR 5069, 31062 Toulouse (France), Fax: (+33) 5-6155-8204Search for more papers by this authorTsuyoshi Kato Dr., Tsuyoshi Kato Dr. [email protected] Université de Toulouse, UPS, LHFA, 118 route de Narbonne, 31062 Toulouse, France, and CNRS, LHFA UMR 5069, 31062 Toulouse (France), Fax: (+33) 5-6155-8204Search for more papers by this authorNathalie Saffon-Merceron Dr., Nathalie Saffon-Merceron Dr. Université de Toulouse, UPS, Structure Fédérative Toulousaine en Chimie Moléculaire, SFTCM FR2599, 118 route de Narbonne, 31062 Toulouse (France)Search for more papers by this authorFernando P. Cossío Prof., Fernando P. Cossío Prof. Departamento de Química Orgínica I, Universidad del País Vasco-Euskal Herriko Unibertsitatea Facultad de Química, P. K. 1072, San Sebastian–Donostia (Spain)Search for more papers by this authorAntoine Baceiredo Dr., Antoine Baceiredo Dr. Université de Toulouse, UPS, LHFA, 118 route de Narbonne, 31062 Toulouse, France, and CNRS, LHFA UMR 5069, 31062 Toulouse (France), Fax: (+33) 5-6155-8204Search for more papers by this author First published: 19 July 2010 https://doi.org/10.1002/chem.201001054Citations: 42Read 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 Stabilising the core: Contrary to the case of non-stabilised transient silylenes, which react with carbonyl compounds to form donor–acceptor adducts, the reaction of a phosphine-coordinated silylene with an aldehyde proceeds by a concerted [2+1] cycloaddition with a very low energy barrier to afford a pentacoordinate oxasilirane (see scheme). This result clearly demonstrates the behaviour of phosphonium sila–ylides as nucleophilic silylenoids. 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_201001054_sm_miscellaneous_information.pdf146.7 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 1M. Weidenbruch, Angew. Chem. 2006, 118, 4347; Angew. Chem. Int. Ed. 2006, 45, 4241. 2For accounts and reviews on the reactivity of transient sila–ylides, see: 2aK. Tamao, M. Asahara, T. Saeki, A. Toshimitsu; T. Saeki, K. Tamao, J. Am. Chem. Soc. 2001, 123, 9210–9211, J. Organomet. Chem. 2000, 600, 118–123; 2bK. Tamao, A. Kawachi, M. Asahara, A. Toshimitsu, Pure Appl. Chem. 1999, 71, 393; 2cA. Toshimitsu, T. Saeki, K. Tamao, Phosphorus Sulfur Silicon Relat. Elem. 2002, 177, 1409. 3 3aC. W. So, H. W. Roesky, J. Magull, E. B. Oswald, Angew. Chem. 2006, 118, 4052; Angew. Chem. Int. Ed. 2006, 45, 3948; 3bC. W. So, H. W. Roesky, P. M. 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Chem. 1996, 61, 3315. 14Only two pentacoordinate silicon-containing three-membered rings are known to date, see: 14aN. W. Mitzel, U. Losehand, J. Am. Chem. Soc. 1998, 120, 7320; 14bK. Naganuma, T. Kawashima, J. Organomet. Chem. 2002, 643–644, 504. 15D. Kost, I. Kalikhman, The Chemistry of Organic Silicon Compounds, Vol. 2, Part 3 (Eds.: ), Wiley, New York, 1998, p. 1339. 16CCDC-766291 (2) and 766292 (8) contain 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. 17H. H. Karsch, R. Richter, E. Witt, J. Organomet. Chem. 1996, 521, 185. 18W. Ando, Y. Hamada, A. Sekiguchi, Tetrahedron Lett. 1982, 23, 5323. 19Gaussian 03, Revision E.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. 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Pople, Gaussian, Inc., Wallingford CT, 2004. 20The reaction to form the P,O-apical 5 is slightly unfavoured due to a higher activation energy (ΔEa=4.3 kcal mol−1). See Scheme S1 of the Supporting Information. 21Ea: Internal energy of the reaction. Gibbs energies of activation for the reactions of sila–ylides are also found to be similar (ΔGa=10.6 (4 a), 9.9 (4 b), 10.1 kcal mol−1 (4 c)). 22The α,β-ambiphilic reactivity of phosphonium sila–ylides with acetylenes was postulated, see: A. Toshimitsu; T. Saeki, K. Tamao, J. Am. Chem. Soc. 2001, 123, 9210–9211. 23The α,β-ambiphilic reactivity is often observed for classical phosphonium ylides, see: 23aO. I. Kolodiazhnyi, Phosphorus Ylides: Chemistry and Application in Organic Synthesis, Wiley-VCH, Weinheim, 1999; 23bA. D. Abell, M. K. Edmonds Organophosphorus Reagents (Ed.: ), Oxford University Press, Oxford, 2004, p. 99. 24D. Seyferth, T. F. O. Lim, J. Am. Chem. Soc. 1978, 100, 7074. 25H. Amii, K. Uneyama, Chem. Rev. 2009, 109, 2119. 26 26aA. G. Brook, Acc. Chem. Res. 1974, 7, 77; 26bN. H. Morgon, A. B. Argenton, M. L. P. da Silva, J. M. Riveros, J. Am. Chem. Soc. 1997, 119, 1708; 26cH. Ikeda, S. J. Inagaki, J. Phys. Chem. A 2001, 105, 10711; 26dY. Wang, M. Dolg, Tetrahedron 1999, 55, 12751. Citing Literature Volume16, Issue28July 26, 2010Pages 8255-8258 ReferencesRelatedInformation