Catalyst-Free Transfer Hydrogenation from Amine-Borane Small Oligomers
Louis Le Moigne1, Tommaso Posenato2, David Gajan3
1Univ Lyon, Université Claude Bernard Lyon 1, CNRS, CNES, ArianeGroup, LHCEP, UMR 5278, Bât. Raulin, 2 rue Victor Grignard, 69622, Villeurbanne, France.
Abstract:
Amine-borane dimers and oligomers with varied steric and electronic profiles were prepared via capping agent-controlled AA/BB polycondensations. They were used for transfer hydrogenations to aldehydes, ketones, imines as well as electron-poor alkene/alkyne moieties. The amine-borane Lewis-paired oligomers and the congested bis(amine-borane)s provided the highest yields. This was likely helped by facilitated dissociation (oligomers) or H-bond assistance. In the case of the oligomers, the second equivalent of H2 present was also engaged in the reaction. Solid-state NMR characterization provides evidence that the boron-containing materials obtained after transfer dehydrogenation are highly similar to those obtained from thermal dehydrogenation. The oligomers bridge the gap between simple amine-borane molecular reductants and the poly-amine-boranes and provide a full picture of the reactivity changes at the different scales.
More Related Videos
08:40Synthesis of Metal Nanoparticles Supported on Carbon Nanotube with Doped Co and N Atoms and its Catalytic Applications in Hydrogen Production
Published on: December 6, 2021
07:06A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis
Published on: February 16, 2020
Related Concept Videos
03:08Hydroboration-Oxidation of Alkenes
02:17Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
02:24Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
02:47Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
02:36Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
02:13Reduction of Alkenes: Catalytic Hydrogenation
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...