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Influence of Ring Strain on the Formation of Rearrangement vs Cyclization Isotwistane Products in the Acyl Radical Reaction of Bicyclo[2.2.2]octanone
[Image: see text] An acyl radical reaction of bicyclo[2.2.2]octenone to yield either rearranged or cyclized isotwistane products is described. The influence of ring strain on the reaction was demonstrated by alternating the sizes of the fused ring in the starting material. DFT calculations showed th...
| Autores principales: | , , , , , , |
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| Formato: | Online Artículo Texto |
| Lenguaje: | English |
| Publicado: |
American Chemical Society
2023
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| Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10630961/ https://www.ncbi.nlm.nih.gov/pubmed/37738398 http://dx.doi.org/10.1021/acs.orglett.3c02374 |
| _version_ | 1785146063824355328 |
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| author | Chen, Chih-Ming Lin, Sheng-Kuo Hsieh, Chi-Tien Reddy, Julakanti Satyanarayana Teoh, Yi Ning Cheng, Mu-Jeng Hsieh, Hsing-Pang |
| author_facet | Chen, Chih-Ming Lin, Sheng-Kuo Hsieh, Chi-Tien Reddy, Julakanti Satyanarayana Teoh, Yi Ning Cheng, Mu-Jeng Hsieh, Hsing-Pang |
| author_sort | Chen, Chih-Ming |
| collection | PubMed |
| description | [Image: see text] An acyl radical reaction of bicyclo[2.2.2]octenone to yield either rearranged or cyclized isotwistane products is described. The influence of ring strain on the reaction was demonstrated by alternating the sizes of the fused ring in the starting material. DFT calculations showed that the reaction is under thermodynamic control and proceeds via a 5-exo-trig cyclization intermediate, which undergoes either hydrogen-atom transfer (HAT) to give a cyclized product or rearrangement via a twistane intermediate to give a rearranged product. |
| format | Online Article Text |
| id | pubmed-10630961 |
| institution | National Center for Biotechnology Information |
| language | English |
| publishDate | 2023 |
| publisher | American Chemical Society |
| record_format | MEDLINE/PubMed |
| spelling | pubmed-106309612023-11-15 Influence of Ring Strain on the Formation of Rearrangement vs Cyclization Isotwistane Products in the Acyl Radical Reaction of Bicyclo[2.2.2]octanone Chen, Chih-Ming Lin, Sheng-Kuo Hsieh, Chi-Tien Reddy, Julakanti Satyanarayana Teoh, Yi Ning Cheng, Mu-Jeng Hsieh, Hsing-Pang Org Lett [Image: see text] An acyl radical reaction of bicyclo[2.2.2]octenone to yield either rearranged or cyclized isotwistane products is described. The influence of ring strain on the reaction was demonstrated by alternating the sizes of the fused ring in the starting material. DFT calculations showed that the reaction is under thermodynamic control and proceeds via a 5-exo-trig cyclization intermediate, which undergoes either hydrogen-atom transfer (HAT) to give a cyclized product or rearrangement via a twistane intermediate to give a rearranged product. American Chemical Society 2023-09-22 /pmc/articles/PMC10630961/ /pubmed/37738398 http://dx.doi.org/10.1021/acs.orglett.3c02374 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
| spellingShingle | Chen, Chih-Ming Lin, Sheng-Kuo Hsieh, Chi-Tien Reddy, Julakanti Satyanarayana Teoh, Yi Ning Cheng, Mu-Jeng Hsieh, Hsing-Pang Influence of Ring Strain on the Formation of Rearrangement vs Cyclization Isotwistane Products in the Acyl Radical Reaction of Bicyclo[2.2.2]octanone |
| title | Influence of
Ring Strain on the Formation of Rearrangement
vs Cyclization Isotwistane Products in the Acyl Radical Reaction of
Bicyclo[2.2.2]octanone |
| title_full | Influence of
Ring Strain on the Formation of Rearrangement
vs Cyclization Isotwistane Products in the Acyl Radical Reaction of
Bicyclo[2.2.2]octanone |
| title_fullStr | Influence of
Ring Strain on the Formation of Rearrangement
vs Cyclization Isotwistane Products in the Acyl Radical Reaction of
Bicyclo[2.2.2]octanone |
| title_full_unstemmed | Influence of
Ring Strain on the Formation of Rearrangement
vs Cyclization Isotwistane Products in the Acyl Radical Reaction of
Bicyclo[2.2.2]octanone |
| title_short | Influence of
Ring Strain on the Formation of Rearrangement
vs Cyclization Isotwistane Products in the Acyl Radical Reaction of
Bicyclo[2.2.2]octanone |
| title_sort | influence of
ring strain on the formation of rearrangement
vs cyclization isotwistane products in the acyl radical reaction of
bicyclo[2.2.2]octanone |
| url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10630961/ https://www.ncbi.nlm.nih.gov/pubmed/37738398 http://dx.doi.org/10.1021/acs.orglett.3c02374 |
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