Synthetic scope and DFT analysis of the chiral binap–gold(I) complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes

The 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 Nat...

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Autores principales: Martín-Rodríguez, María, Castelló, Luis M, Nájera, Carmen, Sansano, José M, Larrañaga, Olatz, de Cózar, Abel, Cossío, Fernando P
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Beilstein-Institut 2013
Materias:
Full Research Paper
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3869218/
https://www.ncbi.nlm.nih.gov/pubmed/24367409
http://dx.doi.org/10.3762/bjoc.9.280
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author Martín-Rodríguez, María
Castelló, Luis M
Nájera, Carmen
Sansano, José M
Larrañaga, Olatz
de Cózar, Abel
Cossío, Fernando P
author_facet Martín-Rodríguez, María
Castelló, Luis M
Nájera, Carmen
Sansano, José M
Larrañaga, Olatz
de Cózar, Abel
Cossío, Fernando P
author_sort Martín-Rodríguez, María
collection PubMed
description The 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.
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spelling pubmed-38692182013-12-23 Synthetic scope and DFT analysis of the chiral binap–gold(I) complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes Martín-Rodríguez, María Castelló, Luis M Nájera, Carmen Sansano, José M Larrañaga, Olatz de Cózar, Abel Cossío, Fernando P Beilstein J Org Chem Full Research Paper The 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. Beilstein-Institut 2013-11-11 /pmc/articles/PMC3869218/ /pubmed/24367409 http://dx.doi.org/10.3762/bjoc.9.280 Text en Copyright © 2013, Martín-Rodríguez et al. https://creativecommons.org/licenses/by/2.0https://www.beilstein-journals.org/bjoc/termsThis is an Open Access article under the terms of the Creative Commons Attribution License (https://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: (https://www.beilstein-journals.org/bjoc/terms)
spellingShingle Full Research Paper
Martín-Rodríguez, María
Castelló, Luis M
Nájera, Carmen
Sansano, José M
Larrañaga, Olatz
de Cózar, Abel
Cossío, Fernando P
Synthetic scope and DFT analysis of the chiral binap–gold(I) complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes
title Synthetic scope and DFT analysis of the chiral binap–gold(I) complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes
title_full Synthetic scope and DFT analysis of the chiral binap–gold(I) complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes
title_fullStr Synthetic scope and DFT analysis of the chiral binap–gold(I) complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes
title_full_unstemmed Synthetic scope and DFT analysis of the chiral binap–gold(I) complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes
title_short Synthetic scope and DFT analysis of the chiral binap–gold(I) complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes
title_sort synthetic scope and dft analysis of the chiral binap–gold(i) complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes
topic Full Research Paper
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3869218/
https://www.ncbi.nlm.nih.gov/pubmed/24367409
http://dx.doi.org/10.3762/bjoc.9.280
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