Search results for "hydrogenation"

Palladium on Charcoal as a Catalyst for Stoichiometric Chemo- and Stereoselective Hydrosilylations and Hydrogenations with Triethylsilane

2014

Stoichiometric quantities of triethylsilane in the presence of activated Pd/C as the catalyst can be used to effect chemo-, regio-, and stereoselective hydrosilylation and transfer hydrogenation reactions. α,β-Unsaturated aldehydes and ketones are selectively hydrosilylated to give the corresponding enol silanes or transfer hydrogenated to give the saturated carbonyl compounds in the presence of other reducible functional groups.

3,4-Dihydro-2H-pyrrole-2-carbonitriles: Useful Intermediates in the Synthesis of Fused Pyrroles and 2,2′-Bipyrroles

2016

Various heterocyclic structures containing the pyrrole moiety have been synthesized from easily accessible 3,4-dihydro-2H-pyrrole-2-carbonitriles in one-pot procedures. 5,6,7,8-Tetrahydroindolizines, 2,3-dihydro-1H-pyrrolizines as well as 6,7,8,9-tetrahydro-5H-pyrrolo[1,2-a]azepines were obtained from these precursors in high yields in an alkylation/annulation sequence. The same conditions were applied in the synthesis of a 5,8-dihydroindolizine, which could easily be transformed to the corresponding indolizine by dehydrogenation. Furthermore, oxidative couplings of 3,4-dihydro-2H-pyrrole-2-carbonitriles with copper(II)-salts furnished 2,2'-bipyrroles as well as 5,5'-bis(5-cyano-1-pyrroline…

A metal-free and regioselective approach to (Z)-β-fluorovinyl sulfones and their chemoselective hydrogenation to β-fluoroalkyl sulfones

2018

Abstract A highly regioselective, metal-free hydrofluorination reaction of alkynyl sulfones was developed using TBAF—one of the cheapest and most commonly available fluoride sources. In addition, the reactivity of the resulting β-fluorovinyl sulfones was studied, focusing on their selective hydrogenation reaction. Both β-fluorovinyl sulfones and their hydrogenation products β-fluoroalkyl sulfones may find applications in medicinal and agrochemical sciences.

Selective Formation of 4,4'-Biphenols by Anodic Dehydrogenative Cross- and Homo-Coupling Reaction.

2019

A simple and selective electrochemical synthesis by dehydrogenative coupling of unprotected 2,6- or 2,5-substituted phenols to the desired 4,4'-biphenols is reported. Using electricity as the oxidizing reagent avoids pre-functionalization of the starting materials, since a selective activation of the substrates takes place. Without the necessity for metal-catalysts or the use of stoichiometric reagents it is an economic and environmentally friendly transformation. The elaborated electrochemical protocol leads to a broad variety of the desired 4,4'-biphenols in a very simplified manner compared to classical approaches. This is particular the case for the cross-coupled products.

Hydrogenation of White Phosphorus to Phosphane with Rhodium and Iridium Trihydrides.

1998

Only one of the four P atoms of P4 reacts with rhodium and iridium trihydrides [(triphos)MH3 ] to provide phosphane [Eq. (a)]. The resulting cyclo-P3 fragment is efficiently scavenged by the metal fragment to give the complexes [(triphos)M(η3 -P3 )]. A mechanism accounting for the hydrogenation reaction is proposed in which the complexes [(triphos)MH(η1 :η1 -P4 )] and [(triphos)M(η1 :η2 -HP4 ] are intermediates. The latter complex contains the unprecedented hydridotetraphosphane ligand HP4- .

Metal‐ and Reagent‐Free Anodic Dehydrogenative Cross‐Coupling of Naphthylamines with Phenols

2018

Optically Active Titanium Complexes Containing Linked Amido‐cyclopentadienyl Ligands: Their Use as Asymmetric Hydrogenation Catalysts

1996

Optically active titanium complexes of the formula Ti(η5:η1−C5R4SiMe2NCHMePh)Cl2 (R = H, Me), containing the cyclopentadienyl ligand linked to a chiral 1-phenylethylamido moiety, were synthesized and characterized in both enantiomerically pure forms. A single-crystal X-ray structural analysis of (S)()Ti(η5:η1−C5H4SiMe2NCHMePh)Cl2 shows a conformation in which the phenyl group is turned away from the metal center. NOE measurements suggest that a related structure is retained in solution. Upon activation with n-butyllithium, these complexes show hydrogenation activity toward imines with slight enantioselectivity.

Diels-alder reactions of methyl- and π-acceptor-substituted 2-vinylindoles with dimethyl acetylenedicarboxylate and tetracyanoethylene: Novel functio…

1991

The Diels-Alder reactions of the 2-vinylindoles 1a-1d, which are now readily accessible, with dimethyl acetylenedicarboxylate and tetracyanoethylene give rise to the novel 1,2-dihydro- and 1,2,3,4-tetrahydrocarbazoles 2, 4, and 5 as well as the fully aromatized carbazoles 3. With regard to the product spectrum, the mechanistic rationale comprises a Diels-Alder step, formal 1,3-hydrogen shift, ene reaction, and dehydrogenation. Conformational aspects of the 1,2-dihydrocarbazoles 2b and 2c are also discussed.

Intermolecular oxidative dehydrogenative 3,3′-coupling of benzo[b]furans and benzo[b]thiophenes promoted by DDQ/H+: total synthesis of shandougenine B

2016

With an excess of a strong acid, 2,3-dichloro-5,6-dicyano-1,4-quinone (DDQ) is shown to promote metal-free intermolecular oxidative dehydrogenative (ODH) 3,3'-coupling of 2-aryl-benzo[b]furans and 2-aryl-benzo[b]thiophenes up to 92% yield as demonstrated with 9 substrates. Based on the analysis of oxidation potentials and molecular orbitals combined with EPR, NMR and UV-Vis observations, the studied reaction is initiated by a DDQ-substrate charge transfer complex and presumably proceeds via oxidation of the substrate into an electrophilic radical cation that further reacts with another molecule of a neutral substrate. The coupling reactivity can easily be predicted from the oxidation potent…

The nickel-support interaction as determining factor of the selectivity to ethylene in the oxidative dehydrogenation of ethane over nickel oxide/alum…

2021

[EN] Nickel oxides supported on gamma-alumina (Ni-loading from 5 to 30 wt% NiO) have been synthesized and tested in the oxidative dehydrogenation (ODH) of ethane in order to determine the importance of the NiO-support interaction. The best performance was achieved by the catalyst with 15 wt% NiO; higher NiO-loadings lead to the formation of unselective bulk-like NiO and lower Ni-loadings present high proportion of free alumina surface sites. The presence of oxalic acid and/or niobium in the synthesis gel resulted in the formation of NiO particles with similar size, but higher crystallinity and reducibility than the standard 15 wt% NiO catalyst. The obtained results have revealed that, in ad…