Highly versatile catalytic hydrogenation of carboxylic and carbonic acid derivatives using a Ru-triphos complex:molecular control over selectivity and substrate scope
The complex [Ru(Triphos)(TMM)] (Triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane, TMM = trimethylene methane) provides an efficient catalytic system for the hydrogenation of a broad range of challenging functionalities encompassing carboxylic esters, amides, carboxylic acids, carbonates, and urea...
Published in: | Journal of the American Chemical Society |
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Language: | English |
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2014
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Online Access: | https://research-portal.st-andrews.ac.uk/en/researchoutput/highly-versatile-catalytic-hydrogenation-of-carboxylic-and-carbonic-acid-derivatives-using-a-rutriphos-complex(2f0045ca-064b-4d6f-94c3-d7fdd3696614).html https://doi.org/10.1021/ja506023f http://pubs.acs.org/doi/suppl/10.1021/ja506023f |
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ftunstandrewcris:oai:research-portal.st-andrews.ac.uk:publications/2f0045ca-064b-4d6f-94c3-d7fdd3696614 2024-06-23T07:52:04+00:00 Highly versatile catalytic hydrogenation of carboxylic and carbonic acid derivatives using a Ru-triphos complex:molecular control over selectivity and substrate scope Vom Stein, T. Meuresch, M. Limper, D. Schmitz, M. Hölscher, M. Coetzee, J. Cole-Hamilton, D.J. Klankermayer, J. Leitner, W. 2014-09-24 https://research-portal.st-andrews.ac.uk/en/researchoutput/highly-versatile-catalytic-hydrogenation-of-carboxylic-and-carbonic-acid-derivatives-using-a-rutriphos-complex(2f0045ca-064b-4d6f-94c3-d7fdd3696614).html https://doi.org/10.1021/ja506023f http://pubs.acs.org/doi/suppl/10.1021/ja506023f eng eng https://research-portal.st-andrews.ac.uk/en/researchoutput/highly-versatile-catalytic-hydrogenation-of-carboxylic-and-carbonic-acid-derivatives-using-a-rutriphos-complex(2f0045ca-064b-4d6f-94c3-d7fdd3696614).html info:eu-repo/semantics/restrictedAccess Vom Stein , T , Meuresch , M , Limper , D , Schmitz , M , Hölscher , M , Coetzee , J , Cole-Hamilton , D J , Klankermayer , J & Leitner , W 2014 , ' Highly versatile catalytic hydrogenation of carboxylic and carbonic acid derivatives using a Ru-triphos complex : molecular control over selectivity and substrate scope ' , Journal of the American Chemical Society , vol. 136 , no. 38 , pp. 13217-13225 . https://doi.org/10.1021/ja506023f article 2014 ftunstandrewcris https://doi.org/10.1021/ja506023f 2024-06-13T00:46:22Z The complex [Ru(Triphos)(TMM)] (Triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane, TMM = trimethylene methane) provides an efficient catalytic system for the hydrogenation of a broad range of challenging functionalities encompassing carboxylic esters, amides, carboxylic acids, carbonates, and urea derivatives. The key control factor for this unique substrate scope results from selective activation to generate either the neutral species [Ru(Triphos)(Solvent)H 2 ] or the cationic intermediate [Ru(Triphos)(Solvent)(H)(H 2 )] + in the presence of an acid additive. Multinuclear NMR spectroscopic studies demonstrated together with DFT investigations that the neutral species generally provides lower energy pathways for the multistep reduction cascades comprising hydrogen transfer to C═O groups and C–O bond cleavage. Carboxylic esters, lactones, anhydrides, secondary amides, and carboxylic acids were hydrogenated in good to excellent yields under these conditions. The formation of the catalytically inactive complexes [Ru(Triphos)(CO)H 2 ] and [Ru(Triphos)(μ-H)] 2 was identified as major deactivation pathways. The former complex results from substrate-dependent decarbonylation and constitutes a major limitation for the substrate scope under the neutral conditions. The deactivation via the carbonyl complex can be suppressed by addition of catalytic amounts of acids comprising non-coordinating anions such as HNTf 2 (bis(trifluoromethane)sulfonimide). Although the corresponding cationic cycle shows higher overall barriers of activation, it provides a powerful hydrogenation pathway at elevated temperatures, enabling the selective reduction of primary amides, carbonates, and ureas in high yields. Thus, the complex [Ru(Triphos)(TMM)] provides a unique platform for the rational selection of reaction conditions for the selective hydrogenation of challenging functional groups and opens novel synthetic pathways for the utilization of renewable carbon sources. Article in Journal/Newspaper Carbonic acid University of St Andrews: Research Portal Journal of the American Chemical Society 136 38 13217 13225 |
institution |
Open Polar |
collection |
University of St Andrews: Research Portal |
op_collection_id |
ftunstandrewcris |
language |
English |
description |
The complex [Ru(Triphos)(TMM)] (Triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane, TMM = trimethylene methane) provides an efficient catalytic system for the hydrogenation of a broad range of challenging functionalities encompassing carboxylic esters, amides, carboxylic acids, carbonates, and urea derivatives. The key control factor for this unique substrate scope results from selective activation to generate either the neutral species [Ru(Triphos)(Solvent)H 2 ] or the cationic intermediate [Ru(Triphos)(Solvent)(H)(H 2 )] + in the presence of an acid additive. Multinuclear NMR spectroscopic studies demonstrated together with DFT investigations that the neutral species generally provides lower energy pathways for the multistep reduction cascades comprising hydrogen transfer to C═O groups and C–O bond cleavage. Carboxylic esters, lactones, anhydrides, secondary amides, and carboxylic acids were hydrogenated in good to excellent yields under these conditions. The formation of the catalytically inactive complexes [Ru(Triphos)(CO)H 2 ] and [Ru(Triphos)(μ-H)] 2 was identified as major deactivation pathways. The former complex results from substrate-dependent decarbonylation and constitutes a major limitation for the substrate scope under the neutral conditions. The deactivation via the carbonyl complex can be suppressed by addition of catalytic amounts of acids comprising non-coordinating anions such as HNTf 2 (bis(trifluoromethane)sulfonimide). Although the corresponding cationic cycle shows higher overall barriers of activation, it provides a powerful hydrogenation pathway at elevated temperatures, enabling the selective reduction of primary amides, carbonates, and ureas in high yields. Thus, the complex [Ru(Triphos)(TMM)] provides a unique platform for the rational selection of reaction conditions for the selective hydrogenation of challenging functional groups and opens novel synthetic pathways for the utilization of renewable carbon sources. |
format |
Article in Journal/Newspaper |
author |
Vom Stein, T. Meuresch, M. Limper, D. Schmitz, M. Hölscher, M. Coetzee, J. Cole-Hamilton, D.J. Klankermayer, J. Leitner, W. |
spellingShingle |
Vom Stein, T. Meuresch, M. Limper, D. Schmitz, M. Hölscher, M. Coetzee, J. Cole-Hamilton, D.J. Klankermayer, J. Leitner, W. Highly versatile catalytic hydrogenation of carboxylic and carbonic acid derivatives using a Ru-triphos complex:molecular control over selectivity and substrate scope |
author_facet |
Vom Stein, T. Meuresch, M. Limper, D. Schmitz, M. Hölscher, M. Coetzee, J. Cole-Hamilton, D.J. Klankermayer, J. Leitner, W. |
author_sort |
Vom Stein, T. |
title |
Highly versatile catalytic hydrogenation of carboxylic and carbonic acid derivatives using a Ru-triphos complex:molecular control over selectivity and substrate scope |
title_short |
Highly versatile catalytic hydrogenation of carboxylic and carbonic acid derivatives using a Ru-triphos complex:molecular control over selectivity and substrate scope |
title_full |
Highly versatile catalytic hydrogenation of carboxylic and carbonic acid derivatives using a Ru-triphos complex:molecular control over selectivity and substrate scope |
title_fullStr |
Highly versatile catalytic hydrogenation of carboxylic and carbonic acid derivatives using a Ru-triphos complex:molecular control over selectivity and substrate scope |
title_full_unstemmed |
Highly versatile catalytic hydrogenation of carboxylic and carbonic acid derivatives using a Ru-triphos complex:molecular control over selectivity and substrate scope |
title_sort |
highly versatile catalytic hydrogenation of carboxylic and carbonic acid derivatives using a ru-triphos complex:molecular control over selectivity and substrate scope |
publishDate |
2014 |
url |
https://research-portal.st-andrews.ac.uk/en/researchoutput/highly-versatile-catalytic-hydrogenation-of-carboxylic-and-carbonic-acid-derivatives-using-a-rutriphos-complex(2f0045ca-064b-4d6f-94c3-d7fdd3696614).html https://doi.org/10.1021/ja506023f http://pubs.acs.org/doi/suppl/10.1021/ja506023f |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
Vom Stein , T , Meuresch , M , Limper , D , Schmitz , M , Hölscher , M , Coetzee , J , Cole-Hamilton , D J , Klankermayer , J & Leitner , W 2014 , ' Highly versatile catalytic hydrogenation of carboxylic and carbonic acid derivatives using a Ru-triphos complex : molecular control over selectivity and substrate scope ' , Journal of the American Chemical Society , vol. 136 , no. 38 , pp. 13217-13225 . https://doi.org/10.1021/ja506023f |
op_relation |
https://research-portal.st-andrews.ac.uk/en/researchoutput/highly-versatile-catalytic-hydrogenation-of-carboxylic-and-carbonic-acid-derivatives-using-a-rutriphos-complex(2f0045ca-064b-4d6f-94c3-d7fdd3696614).html |
op_rights |
info:eu-repo/semantics/restrictedAccess |
op_doi |
https://doi.org/10.1021/ja506023f |
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Journal of the American Chemical Society |
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136 |
container_issue |
38 |
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