DFT Studies on the Mechanism of the Iridium-Catalyzed Formal [4 + 1] Cycloaddition of Biphenylene with Alkenes

[Image: see text] Recently, we reported an Ir-catalyzed formal [4 + 1] cycloaddition of biphenylenes with alkenes, which gave 9,9-disubstituted fluorenes in moderate to excellent yields. We proposed a reaction mechanism that involved the intermolecular insertion of alkenes, β-elimination, and intram...

Descripción completa

Detalles Bibliográficos
Autores principales: Takano, Hideaki, Sugimura, Natsuhiko, Kanyiva, Kyalo Stephen, Shibata, Takanori
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2017
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6641719/
https://www.ncbi.nlm.nih.gov/pubmed/31457794
http://dx.doi.org/10.1021/acsomega.7b00403
_version_ 1783436838515507200
author Takano, Hideaki
Sugimura, Natsuhiko
Kanyiva, Kyalo Stephen
Shibata, Takanori
author_facet Takano, Hideaki
Sugimura, Natsuhiko
Kanyiva, Kyalo Stephen
Shibata, Takanori
author_sort Takano, Hideaki
collection PubMed
description [Image: see text] Recently, we reported an Ir-catalyzed formal [4 + 1] cycloaddition of biphenylenes with alkenes, which gave 9,9-disubstituted fluorenes in moderate to excellent yields. We proposed a reaction mechanism that involved the intermolecular insertion of alkenes, β-elimination, and intramolecular insertion based on the results of experimental mechanistic studies. Herein, we further support the proposed mechanism by density functional theory calculations and explain why [4 + 1] cycloaddition proceeds rather than conventional [4 + 2] cycloaddition.
format Online
Article
Text
id pubmed-6641719
institution National Center for Biotechnology Information
language English
publishDate 2017
publisher American Chemical Society
record_format MEDLINE/PubMed
spelling pubmed-66417192019-08-27 DFT Studies on the Mechanism of the Iridium-Catalyzed Formal [4 + 1] Cycloaddition of Biphenylene with Alkenes Takano, Hideaki Sugimura, Natsuhiko Kanyiva, Kyalo Stephen Shibata, Takanori ACS Omega [Image: see text] Recently, we reported an Ir-catalyzed formal [4 + 1] cycloaddition of biphenylenes with alkenes, which gave 9,9-disubstituted fluorenes in moderate to excellent yields. We proposed a reaction mechanism that involved the intermolecular insertion of alkenes, β-elimination, and intramolecular insertion based on the results of experimental mechanistic studies. Herein, we further support the proposed mechanism by density functional theory calculations and explain why [4 + 1] cycloaddition proceeds rather than conventional [4 + 2] cycloaddition. American Chemical Society 2017-08-30 /pmc/articles/PMC6641719/ /pubmed/31457794 http://dx.doi.org/10.1021/acsomega.7b00403 Text en Copyright © 2017 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Takano, Hideaki
Sugimura, Natsuhiko
Kanyiva, Kyalo Stephen
Shibata, Takanori
DFT Studies on the Mechanism of the Iridium-Catalyzed Formal [4 + 1] Cycloaddition of Biphenylene with Alkenes
title DFT Studies on the Mechanism of the Iridium-Catalyzed Formal [4 + 1] Cycloaddition of Biphenylene with Alkenes
title_full DFT Studies on the Mechanism of the Iridium-Catalyzed Formal [4 + 1] Cycloaddition of Biphenylene with Alkenes
title_fullStr DFT Studies on the Mechanism of the Iridium-Catalyzed Formal [4 + 1] Cycloaddition of Biphenylene with Alkenes
title_full_unstemmed DFT Studies on the Mechanism of the Iridium-Catalyzed Formal [4 + 1] Cycloaddition of Biphenylene with Alkenes
title_short DFT Studies on the Mechanism of the Iridium-Catalyzed Formal [4 + 1] Cycloaddition of Biphenylene with Alkenes
title_sort dft studies on the mechanism of the iridium-catalyzed formal [4 + 1] cycloaddition of biphenylene with alkenes
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6641719/
https://www.ncbi.nlm.nih.gov/pubmed/31457794
http://dx.doi.org/10.1021/acsomega.7b00403
work_keys_str_mv AT takanohideaki dftstudiesonthemechanismoftheiridiumcatalyzedformal41cycloadditionofbiphenylenewithalkenes
AT sugimuranatsuhiko dftstudiesonthemechanismoftheiridiumcatalyzedformal41cycloadditionofbiphenylenewithalkenes
AT kanyivakyalostephen dftstudiesonthemechanismoftheiridiumcatalyzedformal41cycloadditionofbiphenylenewithalkenes
AT shibatatakanori dftstudiesonthemechanismoftheiridiumcatalyzedformal41cycloadditionofbiphenylenewithalkenes

Ejemplares similares