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Probing the Hydrogenation of Vinyl Sulfoxides Using para-Hydrogen

[Image: see text] Vinyl sulfoxides are an important functional group used in a wide range of organic transformations. Here, we use [IrCl(COD)(IMes)] where IMes = 1,3-bis(2,4,6-trimethyl-phenyl)imidazole-2-ylidene and COD = cis,cis-1,5-cyclooctadiene to rapidly hydrogenate phenylvinylsulfoxide. We us...

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Autores principales: Tickner, Ben J., Parker, Rachel R., Whitwood, Adrian C., Duckett, Simon B.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2019
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6880776/
https://www.ncbi.nlm.nih.gov/pubmed/31787798
http://dx.doi.org/10.1021/acs.organomet.9b00610
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author Tickner, Ben J.
Parker, Rachel R.
Whitwood, Adrian C.
Duckett, Simon B.
author_facet Tickner, Ben J.
Parker, Rachel R.
Whitwood, Adrian C.
Duckett, Simon B.
author_sort Tickner, Ben J.
collection PubMed
description [Image: see text] Vinyl sulfoxides are an important functional group used in a wide range of organic transformations. Here, we use [IrCl(COD)(IMes)] where IMes = 1,3-bis(2,4,6-trimethyl-phenyl)imidazole-2-ylidene and COD = cis,cis-1,5-cyclooctadiene to rapidly hydrogenate phenylvinylsulfoxide. We use para-hydrogen-induced hyperpolarization (PHIP) to follow this reaction with [IrCl(H)(2)(IMes)(S(O)(Ph)(Et))(2)] dominating in the later stages. Decomposition to form the reduced C–S bond cleavage product [Ir(2)(H)(3)(κ(2)-H)(κ(2)-SPh)(2)(IMes)(2)(S(Et)(Ph)O)] limits turnover. The related product [Ir(2)(H)(4)(κ(2)-S)(IMes)(2)(S(O)(CH(2)Ph)(2))(2)] is formed from dibenzylsulfoxide, demonstrating the wider utility of this transformation.
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spelling pubmed-68807762019-11-29 Probing the Hydrogenation of Vinyl Sulfoxides Using para-Hydrogen Tickner, Ben J. Parker, Rachel R. Whitwood, Adrian C. Duckett, Simon B. Organometallics [Image: see text] Vinyl sulfoxides are an important functional group used in a wide range of organic transformations. Here, we use [IrCl(COD)(IMes)] where IMes = 1,3-bis(2,4,6-trimethyl-phenyl)imidazole-2-ylidene and COD = cis,cis-1,5-cyclooctadiene to rapidly hydrogenate phenylvinylsulfoxide. We use para-hydrogen-induced hyperpolarization (PHIP) to follow this reaction with [IrCl(H)(2)(IMes)(S(O)(Ph)(Et))(2)] dominating in the later stages. Decomposition to form the reduced C–S bond cleavage product [Ir(2)(H)(3)(κ(2)-H)(κ(2)-SPh)(2)(IMes)(2)(S(Et)(Ph)O)] limits turnover. The related product [Ir(2)(H)(4)(κ(2)-S)(IMes)(2)(S(O)(CH(2)Ph)(2))(2)] is formed from dibenzylsulfoxide, demonstrating the wider utility of this transformation. American Chemical Society 2019-11-14 2019-11-25 /pmc/articles/PMC6880776/ /pubmed/31787798 http://dx.doi.org/10.1021/acs.organomet.9b00610 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 Tickner, Ben J.
Parker, Rachel R.
Whitwood, Adrian C.
Duckett, Simon B.
Probing the Hydrogenation of Vinyl Sulfoxides Using para-Hydrogen
title Probing the Hydrogenation of Vinyl Sulfoxides Using para-Hydrogen
title_full Probing the Hydrogenation of Vinyl Sulfoxides Using para-Hydrogen
title_fullStr Probing the Hydrogenation of Vinyl Sulfoxides Using para-Hydrogen
title_full_unstemmed Probing the Hydrogenation of Vinyl Sulfoxides Using para-Hydrogen
title_short Probing the Hydrogenation of Vinyl Sulfoxides Using para-Hydrogen
title_sort probing the hydrogenation of vinyl sulfoxides using para-hydrogen
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6880776/
https://www.ncbi.nlm.nih.gov/pubmed/31787798
http://dx.doi.org/10.1021/acs.organomet.9b00610
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