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Stereodivergent Synthesis of Chiral Fullerenes by [3 + 2] Cycloadditions to C(60)
[Image: see text] A wide range of new dipoles and catalysts have been used in 1,3-dipolar cycloadditions of N-metalated azomethine ylides onto C(60) yielding a full stereodivergent synthesis of pyrrolidino[60]fullerenes with complete diastereoselectivities and very high enantioselectivities. The use...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2013
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3914395/ https://www.ncbi.nlm.nih.gov/pubmed/24359021 http://dx.doi.org/10.1021/ja410408c |
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author | Maroto, Enrique E. Filippone, Salvatore Suárez, Margarita Martínez-Álvarez, Roberto de Cózar, Abel Cossío, Fernando P. Martín, Nazario |
author_facet | Maroto, Enrique E. Filippone, Salvatore Suárez, Margarita Martínez-Álvarez, Roberto de Cózar, Abel Cossío, Fernando P. Martín, Nazario |
author_sort | Maroto, Enrique E. |
collection | PubMed |
description | [Image: see text] A wide range of new dipoles and catalysts have been used in 1,3-dipolar cycloadditions of N-metalated azomethine ylides onto C(60) yielding a full stereodivergent synthesis of pyrrolidino[60]fullerenes with complete diastereoselectivities and very high enantioselectivities. The use of less-explored chiral α-iminoamides as starting 1,3-dipoles leads to an interesting double asymmetric induction resulting in a matching/mismatching effect depending upon the absolute configuration of the stereocenter in the starting α-iminoamide. An enantioselective process was also found in the retrocycloaddition reaction as revealed by mass spectrometry analysis on quasi-enantiomeric pyrrolidino[60]fullerenes. Theoretical DFT calculations are in very good agreement with the experimental data. On the basis of this agreement, a plausible reaction mechanism is proposed. |
format | Online Article Text |
id | pubmed-3914395 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2013 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-39143952014-02-05 Stereodivergent Synthesis of Chiral Fullerenes by [3 + 2] Cycloadditions to C(60) Maroto, Enrique E. Filippone, Salvatore Suárez, Margarita Martínez-Álvarez, Roberto de Cózar, Abel Cossío, Fernando P. Martín, Nazario J Am Chem Soc [Image: see text] A wide range of new dipoles and catalysts have been used in 1,3-dipolar cycloadditions of N-metalated azomethine ylides onto C(60) yielding a full stereodivergent synthesis of pyrrolidino[60]fullerenes with complete diastereoselectivities and very high enantioselectivities. The use of less-explored chiral α-iminoamides as starting 1,3-dipoles leads to an interesting double asymmetric induction resulting in a matching/mismatching effect depending upon the absolute configuration of the stereocenter in the starting α-iminoamide. An enantioselective process was also found in the retrocycloaddition reaction as revealed by mass spectrometry analysis on quasi-enantiomeric pyrrolidino[60]fullerenes. Theoretical DFT calculations are in very good agreement with the experimental data. On the basis of this agreement, a plausible reaction mechanism is proposed. American Chemical Society 2013-12-22 2014-01-15 /pmc/articles/PMC3914395/ /pubmed/24359021 http://dx.doi.org/10.1021/ja410408c Text en Copyright © 2013 American Chemical Society Terms of Use (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) |
spellingShingle | Maroto, Enrique E. Filippone, Salvatore Suárez, Margarita Martínez-Álvarez, Roberto de Cózar, Abel Cossío, Fernando P. Martín, Nazario Stereodivergent Synthesis of Chiral Fullerenes by [3 + 2] Cycloadditions to C(60) |
title | Stereodivergent
Synthesis of Chiral Fullerenes by
[3 + 2] Cycloadditions to C(60) |
title_full | Stereodivergent
Synthesis of Chiral Fullerenes by
[3 + 2] Cycloadditions to C(60) |
title_fullStr | Stereodivergent
Synthesis of Chiral Fullerenes by
[3 + 2] Cycloadditions to C(60) |
title_full_unstemmed | Stereodivergent
Synthesis of Chiral Fullerenes by
[3 + 2] Cycloadditions to C(60) |
title_short | Stereodivergent
Synthesis of Chiral Fullerenes by
[3 + 2] Cycloadditions to C(60) |
title_sort | stereodivergent
synthesis of chiral fullerenes by
[3 + 2] cycloadditions to c(60) |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3914395/ https://www.ncbi.nlm.nih.gov/pubmed/24359021 http://dx.doi.org/10.1021/ja410408c |
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