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Tsuji–Wacker-Type Oxidation beyond Methyl Ketones: Reacting Unprotected Carbohydrate-Based Terminal Olefins through the “Uemura System” to Hemiketals and α,β-Unsaturated Diketones

[Image: see text] Aerobic Pd(AcO)(2)/pyridine-catalyzed oxidation of unprotected carbohydrate-based terminal alkenes was studied. In accordance with previous reports, the initial reaction step gave methyl ketones. However, our substrates partially gave subsequent α,β-water elimination and alcohol ox...

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Autores principales: Runeberg, Patrik A., Eklund, Patrik C.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2019
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7076729/
https://www.ncbi.nlm.nih.gov/pubmed/31557043
http://dx.doi.org/10.1021/acs.orglett.9b02134
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author Runeberg, Patrik A.
Eklund, Patrik C.
author_facet Runeberg, Patrik A.
Eklund, Patrik C.
author_sort Runeberg, Patrik A.
collection PubMed
description [Image: see text] Aerobic Pd(AcO)(2)/pyridine-catalyzed oxidation of unprotected carbohydrate-based terminal alkenes was studied. In accordance with previous reports, the initial reaction step gave methyl ketones. However, our substrates partially gave subsequent α,β-water elimination and alcohol oxidation to α,β-unsaturated 2,5-diketones. Upon increasing the pressure of O(2), the reaction was shifted toward formation of α,β-epoxy-2-ketones. The reactions were stereoselective and gave up to quantitative conversions. However, isolated yields were substantially lower because of the complexity of the product mixtures.
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spelling pubmed-70767292020-03-18 Tsuji–Wacker-Type Oxidation beyond Methyl Ketones: Reacting Unprotected Carbohydrate-Based Terminal Olefins through the “Uemura System” to Hemiketals and α,β-Unsaturated Diketones Runeberg, Patrik A. Eklund, Patrik C. Org Lett [Image: see text] Aerobic Pd(AcO)(2)/pyridine-catalyzed oxidation of unprotected carbohydrate-based terminal alkenes was studied. In accordance with previous reports, the initial reaction step gave methyl ketones. However, our substrates partially gave subsequent α,β-water elimination and alcohol oxidation to α,β-unsaturated 2,5-diketones. Upon increasing the pressure of O(2), the reaction was shifted toward formation of α,β-epoxy-2-ketones. The reactions were stereoselective and gave up to quantitative conversions. However, isolated yields were substantially lower because of the complexity of the product mixtures. American Chemical Society 2019-09-26 2019-10-18 /pmc/articles/PMC7076729/ /pubmed/31557043 http://dx.doi.org/10.1021/acs.orglett.9b02134 Text en Copyright © 2019 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
spellingShingle Runeberg, Patrik A.
Eklund, Patrik C.
Tsuji–Wacker-Type Oxidation beyond Methyl Ketones: Reacting Unprotected Carbohydrate-Based Terminal Olefins through the “Uemura System” to Hemiketals and α,β-Unsaturated Diketones
title Tsuji–Wacker-Type Oxidation beyond Methyl Ketones: Reacting Unprotected Carbohydrate-Based Terminal Olefins through the “Uemura System” to Hemiketals and α,β-Unsaturated Diketones
title_full Tsuji–Wacker-Type Oxidation beyond Methyl Ketones: Reacting Unprotected Carbohydrate-Based Terminal Olefins through the “Uemura System” to Hemiketals and α,β-Unsaturated Diketones
title_fullStr Tsuji–Wacker-Type Oxidation beyond Methyl Ketones: Reacting Unprotected Carbohydrate-Based Terminal Olefins through the “Uemura System” to Hemiketals and α,β-Unsaturated Diketones
title_full_unstemmed Tsuji–Wacker-Type Oxidation beyond Methyl Ketones: Reacting Unprotected Carbohydrate-Based Terminal Olefins through the “Uemura System” to Hemiketals and α,β-Unsaturated Diketones
title_short Tsuji–Wacker-Type Oxidation beyond Methyl Ketones: Reacting Unprotected Carbohydrate-Based Terminal Olefins through the “Uemura System” to Hemiketals and α,β-Unsaturated Diketones
title_sort tsuji–wacker-type oxidation beyond methyl ketones: reacting unprotected carbohydrate-based terminal olefins through the “uemura system” to hemiketals and α,β-unsaturated diketones
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7076729/
https://www.ncbi.nlm.nih.gov/pubmed/31557043
http://dx.doi.org/10.1021/acs.orglett.9b02134
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