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Iodine-Catalyzed Functionalization of Primary Aliphatic Amines to Oxazoles, 1,4-Oxazines, and Oxazinones
[Image: see text] Unprecedented I(2)-catalyzed α,α-C(sp(3))-H, decarboxylative α-C(sp(3))-H, lactonized α-C(sp(3))-H, and α,β-C(sp(3))-H functionalized 5- and 6-annulation as well as α-C(sp(3))-H activated 6-lactonization of primary aliphatic amines are devised under aerobic conditions. The metal-fr...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2019
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6894181/ https://www.ncbi.nlm.nih.gov/pubmed/31815245 http://dx.doi.org/10.1021/acsomega.9b03501 |
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author | Debnath, Sudipto Das, Tuluma Gayen, Subrata Ghosh, Tapas Maiti, Dilip K. |
author_facet | Debnath, Sudipto Das, Tuluma Gayen, Subrata Ghosh, Tapas Maiti, Dilip K. |
author_sort | Debnath, Sudipto |
collection | PubMed |
description | [Image: see text] Unprecedented I(2)-catalyzed α,α-C(sp(3))-H, decarboxylative α-C(sp(3))-H, lactonized α-C(sp(3))-H, and α,β-C(sp(3))-H functionalized 5- and 6-annulation as well as α-C(sp(3))-H activated 6-lactonization of primary aliphatic amines are devised under aerobic conditions. The metal-free sustainable strategy was employed for the diverse construction of valuable five-and six-membered polycyclic N,O-heteroaromatics such as oxazoles, 1,4-oxazines, and oxazin-2-one with a rapid reaction rate and high yield. The viability of this mild nonmetallic catalysis is successfully verified through syntheses of labile chiral heterocyclic analogues. In contrast to the common practice, this method is not limited to use of prefunctionalized amines, directing groups (DGs) and/or transient DGs, metal catalysts, and traditional oxidants. The possible mechanistic pathway of the annulation reaction is investigated by control experiments and ESI-MS data collected for a reaction mixture of the ongoing reaction. The synthesized new compounds are potent organic nanobuilding blocks to achieve valuable organic nanomaterials of different sizes, shapes, and dimensions, which are under investigation for the discovery of high-tech devices of innovative organic nanoelectronics and photophysical properties. |
format | Online Article Text |
id | pubmed-6894181 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-68941812019-12-06 Iodine-Catalyzed Functionalization of Primary Aliphatic Amines to Oxazoles, 1,4-Oxazines, and Oxazinones Debnath, Sudipto Das, Tuluma Gayen, Subrata Ghosh, Tapas Maiti, Dilip K. ACS Omega [Image: see text] Unprecedented I(2)-catalyzed α,α-C(sp(3))-H, decarboxylative α-C(sp(3))-H, lactonized α-C(sp(3))-H, and α,β-C(sp(3))-H functionalized 5- and 6-annulation as well as α-C(sp(3))-H activated 6-lactonization of primary aliphatic amines are devised under aerobic conditions. The metal-free sustainable strategy was employed for the diverse construction of valuable five-and six-membered polycyclic N,O-heteroaromatics such as oxazoles, 1,4-oxazines, and oxazin-2-one with a rapid reaction rate and high yield. The viability of this mild nonmetallic catalysis is successfully verified through syntheses of labile chiral heterocyclic analogues. In contrast to the common practice, this method is not limited to use of prefunctionalized amines, directing groups (DGs) and/or transient DGs, metal catalysts, and traditional oxidants. The possible mechanistic pathway of the annulation reaction is investigated by control experiments and ESI-MS data collected for a reaction mixture of the ongoing reaction. The synthesized new compounds are potent organic nanobuilding blocks to achieve valuable organic nanomaterials of different sizes, shapes, and dimensions, which are under investigation for the discovery of high-tech devices of innovative organic nanoelectronics and photophysical properties. American Chemical Society 2019-11-18 /pmc/articles/PMC6894181/ /pubmed/31815245 http://dx.doi.org/10.1021/acsomega.9b03501 Text en Copyright © 2019 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 | Debnath, Sudipto Das, Tuluma Gayen, Subrata Ghosh, Tapas Maiti, Dilip K. Iodine-Catalyzed Functionalization of Primary Aliphatic Amines to Oxazoles, 1,4-Oxazines, and Oxazinones |
title | Iodine-Catalyzed
Functionalization of Primary Aliphatic
Amines to Oxazoles, 1,4-Oxazines, and Oxazinones |
title_full | Iodine-Catalyzed
Functionalization of Primary Aliphatic
Amines to Oxazoles, 1,4-Oxazines, and Oxazinones |
title_fullStr | Iodine-Catalyzed
Functionalization of Primary Aliphatic
Amines to Oxazoles, 1,4-Oxazines, and Oxazinones |
title_full_unstemmed | Iodine-Catalyzed
Functionalization of Primary Aliphatic
Amines to Oxazoles, 1,4-Oxazines, and Oxazinones |
title_short | Iodine-Catalyzed
Functionalization of Primary Aliphatic
Amines to Oxazoles, 1,4-Oxazines, and Oxazinones |
title_sort | iodine-catalyzed
functionalization of primary aliphatic
amines to oxazoles, 1,4-oxazines, and oxazinones |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6894181/ https://www.ncbi.nlm.nih.gov/pubmed/31815245 http://dx.doi.org/10.1021/acsomega.9b03501 |
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