Synthetic scope and DFT analysis of the chiral binap-gold(I) complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes
| Data(s) |
04/02/2014
04/02/2014
01/11/2013
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| Resumo |
he 1,3-dipolar cycloaddition between glycine-derived azlactones with maleimides is efficiently catalyzed by the dimeric chiral complex [(S-a)-Binap.AuTFA](2). The alanine-derived oxazolone only reacts with tert-butyl acrylate giving anomalous regiochemistry, which is explained and supported by Natural Resonance Theory and Nucleus Independent Chemical Shifts calculations. The origin of the high enantiodiscrimination observed with maleimides and tert-butyl acrylate is analyzed using DFT computed at M06/Lanl2dz//ONIOM(b3lyp/Lanl2dz:UFF) level. Several applications of these cycloadducts in the synthesis of new proline derivatives with a 2,5-trans-arrangement and in the preparation of complex fused polycyclic molecules are described. |
| Identificador |
Beilstein Journal of Organic Chemistry 9 : 2422–2433 (2013) 1860-5397 http://hdl.handle.net/10810/11341 10.3762/bjoc.9.280 |
| Idioma(s) |
eng |
| Publicador |
Beilstein Institut |
| Relação |
http://www.beilstein-journals.org/bjoc/single/articleFullText.htm?publicId=1860-5397-9-280 |
| Direitos |
© 2013 Martín-Rodríguez et al; licensee Beilstein-Institut. This is an Open Access article under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (http://www.beilstein-journals.org/bjoc) info:eu-repo/semantics/openAccess |
| Palavras-Chave | #asymmetric catalysis #DFT #1,3-dipolar cycloaddition #gold catalysis #NICS #NTR #oxazolones #prolines |
| Tipo |
info:eu-repo/semantics/article |
