(Semi)hydrogenation of enoates and alkynes effected by a versatile, particulate copper catalyst

We communicate a versatile and user-friendly Cu-based catalytic method that allows for the selective hydrogenation of enoates and alkynes. The introduced protocol is free from any ex ante modifications of the used Cu(I) precursors by air-sensitive phosphines or elaborate N-heterocyclic carbene ligan...

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Main Authors: Samuel Redl, Christoph Topf
Format: Article
Language:English
Published: Elsevier 2024-12-01
Series:Tetrahedron Chem
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Online Access:http://www.sciencedirect.com/science/article/pii/S2666951X24000287
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author Samuel Redl
Christoph Topf
author_facet Samuel Redl
Christoph Topf
author_sort Samuel Redl
collection DOAJ
description We communicate a versatile and user-friendly Cu-based catalytic method that allows for the selective hydrogenation of enoates and alkynes. The introduced protocol is free from any ex ante modifications of the used Cu(I) precursors by air-sensitive phosphines or elaborate N-heterocyclic carbene ligands. The conjugate hydrogenation of enoates and the (selective) reduction of C≡C bonds is achieved through a [Cu(CH3CN)4]+/tert-butoxide pair whereby we describe a delicate influence of the base cation on the chemoselectivity of the respective transformation. In case of the ester-to-alcohol reduction, a combination of simple CuI and NaOtBu proved to be successful. Deuteration experiments are included to address certain mechanistic aspects of the introduced catalytic system. All requisite chemicals are readily obtainable through commercial channels and the catalyst assembly is set up on the bench without the need for special lab-technical precautions.
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spelling doaj-art-94fccba122624f5a8aefa2eeb570d3bd2025-08-20T02:35:50ZengElsevierTetrahedron Chem2666-951X2024-12-011210008910.1016/j.tchem.2024.100089(Semi)hydrogenation of enoates and alkynes effected by a versatile, particulate copper catalystSamuel Redl0Christoph Topf1Institute of Catalysis (INCA), Johannes Kepler University, Altenbergerstraße 69, 4040, Linz, AustriaCorresponding author.; Institute of Catalysis (INCA), Johannes Kepler University, Altenbergerstraße 69, 4040, Linz, AustriaWe communicate a versatile and user-friendly Cu-based catalytic method that allows for the selective hydrogenation of enoates and alkynes. The introduced protocol is free from any ex ante modifications of the used Cu(I) precursors by air-sensitive phosphines or elaborate N-heterocyclic carbene ligands. The conjugate hydrogenation of enoates and the (selective) reduction of C≡C bonds is achieved through a [Cu(CH3CN)4]+/tert-butoxide pair whereby we describe a delicate influence of the base cation on the chemoselectivity of the respective transformation. In case of the ester-to-alcohol reduction, a combination of simple CuI and NaOtBu proved to be successful. Deuteration experiments are included to address certain mechanistic aspects of the introduced catalytic system. All requisite chemicals are readily obtainable through commercial channels and the catalyst assembly is set up on the bench without the need for special lab-technical precautions.http://www.sciencedirect.com/science/article/pii/S2666951X24000287Heterogeneous hydrogenationSelective reductionCopperN-Heterocyclic carbenesEnoatesAlkynes
spellingShingle Samuel Redl
Christoph Topf
(Semi)hydrogenation of enoates and alkynes effected by a versatile, particulate copper catalyst
Tetrahedron Chem
Heterogeneous hydrogenation
Selective reduction
Copper
N-Heterocyclic carbenes
Enoates
Alkynes
title (Semi)hydrogenation of enoates and alkynes effected by a versatile, particulate copper catalyst
title_full (Semi)hydrogenation of enoates and alkynes effected by a versatile, particulate copper catalyst
title_fullStr (Semi)hydrogenation of enoates and alkynes effected by a versatile, particulate copper catalyst
title_full_unstemmed (Semi)hydrogenation of enoates and alkynes effected by a versatile, particulate copper catalyst
title_short (Semi)hydrogenation of enoates and alkynes effected by a versatile, particulate copper catalyst
title_sort semi hydrogenation of enoates and alkynes effected by a versatile particulate copper catalyst
topic Heterogeneous hydrogenation
Selective reduction
Copper
N-Heterocyclic carbenes
Enoates
Alkynes
url http://www.sciencedirect.com/science/article/pii/S2666951X24000287
work_keys_str_mv AT samuelredl semihydrogenationofenoatesandalkyneseffectedbyaversatileparticulatecoppercatalyst
AT christophtopf semihydrogenationofenoatesandalkyneseffectedbyaversatileparticulatecoppercatalyst