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Catalyst-Free Synthesis of Borylated Lactones from Esters via Electrophilic Oxyboration
[Image: see text] A catalyst-free oxyboration reaction of alkynes is developed. The resulting borylated isocoumarins and 2-pyrones are isolated as boronic acids, pinacolboronate esters, or potassium organotrifluoroborate salts, providing a variety of bench-stable organoboron building blocks for down...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2016
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4768685/ https://www.ncbi.nlm.nih.gov/pubmed/26849770 http://dx.doi.org/10.1021/jacs.5b12989 |
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author | Faizi, Darius J. Issaian, Adena Davis, Ashlee J. Blum, Suzanne A. |
author_facet | Faizi, Darius J. Issaian, Adena Davis, Ashlee J. Blum, Suzanne A. |
author_sort | Faizi, Darius J. |
collection | PubMed |
description | [Image: see text] A catalyst-free oxyboration reaction of alkynes is developed. The resulting borylated isocoumarins and 2-pyrones are isolated as boronic acids, pinacolboronate esters, or potassium organotrifluoroborate salts, providing a variety of bench-stable organoboron building blocks for downstream functionalization. This method has functional group compatibility, is scalable, and proceeds with readily available materials: B-chlorocatecholborane and methyl esters. Mechanistic studies indicate that the B-chlorocatecholborane acts as a carbophilic Lewis acid toward the alkyne, providing a mechanistically distinct pathway for oxyboration that avoids B–O σ bond formation and enables this catalyst-free route. |
format | Online Article Text |
id | pubmed-4768685 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2016 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-47686852017-02-05 Catalyst-Free Synthesis of Borylated Lactones from Esters via Electrophilic Oxyboration Faizi, Darius J. Issaian, Adena Davis, Ashlee J. Blum, Suzanne A. J Am Chem Soc [Image: see text] A catalyst-free oxyboration reaction of alkynes is developed. The resulting borylated isocoumarins and 2-pyrones are isolated as boronic acids, pinacolboronate esters, or potassium organotrifluoroborate salts, providing a variety of bench-stable organoboron building blocks for downstream functionalization. This method has functional group compatibility, is scalable, and proceeds with readily available materials: B-chlorocatecholborane and methyl esters. Mechanistic studies indicate that the B-chlorocatecholborane acts as a carbophilic Lewis acid toward the alkyne, providing a mechanistically distinct pathway for oxyboration that avoids B–O σ bond formation and enables this catalyst-free route. American Chemical Society 2016-02-05 2016-02-24 /pmc/articles/PMC4768685/ /pubmed/26849770 http://dx.doi.org/10.1021/jacs.5b12989 Text en Copyright © 2016 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 | Faizi, Darius J. Issaian, Adena Davis, Ashlee J. Blum, Suzanne A. Catalyst-Free Synthesis of Borylated Lactones from Esters via Electrophilic Oxyboration |
title | Catalyst-Free
Synthesis of Borylated Lactones from
Esters via Electrophilic Oxyboration |
title_full | Catalyst-Free
Synthesis of Borylated Lactones from
Esters via Electrophilic Oxyboration |
title_fullStr | Catalyst-Free
Synthesis of Borylated Lactones from
Esters via Electrophilic Oxyboration |
title_full_unstemmed | Catalyst-Free
Synthesis of Borylated Lactones from
Esters via Electrophilic Oxyboration |
title_short | Catalyst-Free
Synthesis of Borylated Lactones from
Esters via Electrophilic Oxyboration |
title_sort | catalyst-free
synthesis of borylated lactones from
esters via electrophilic oxyboration |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4768685/ https://www.ncbi.nlm.nih.gov/pubmed/26849770 http://dx.doi.org/10.1021/jacs.5b12989 |
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