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Relevant academic research and scientific papers

Electrolysis in the presence of ultrasound: Cell geometries for the application of extreme rates of mass transfer in electrosynthesis

Two types of sonoelectrochemical reactors for preparative synthetic work are suggested and characterized by their performance in the reversible one electron reduction of cobalticenium cations in acetonitrile solution. The dominant effect of ultrasound is

Aryl-substituted dimethylbenzimidazolines as effective reductants of photoinduced electron transfer reactions

Photoinduced electron transfer (PET) reactions promoted by 2-aryl substituted 1,3-dimethylbenzimidazolines (Ar-DMBIH) were investigated. Excited states of Ar-DMBIH, formed by irradiation using light above 360 nm, initiate PET reductions of various organic substrates, including transformations of epoxy ketones to aldols, free radical rearrangements such as the Dowd-Beckwith ring-expansion and 5-exo hexenyl cyclization, deprotection of N-sulfonyl-indols, and allylation of acyl formates. In these processes, Ar-DMBIH possessing 1-naphthyl, 2-naphthyl, 1-pyrenyl and 9-anthryl substituents formally act as two electron and one proton donors while the hydroxynaphthyl substituted derivative serves as a two electron and two proton donor. On the basis of the results of absorption spectroscopy studies, cyclic voltammetry and DFT calculation, a mechanistic sequence for these reduction reactions is proposed that involves initial photoexcitation of the aryl chromophore of the Ar-DMBIH followed by single electron transfer (SET) to the organic substrate to generate the radical cation of benzimidazoline and the radical anion of the substrate.

Photoinduced electron-transfer systems consisting of electron-donating pyrenes or anthracenes and benzimidazolines for reductive transformation of carbonyl compounds

Photoinduced electron-transfer reactions of several ketone substrates were studied to evaluate the utilities of 1,6-bis(dimethylamino)pyrene (BDMAP), 1,6-dimethoxypyrene (DMP), 9,10-bis(dimethylamino)anthracene (BDMAA), and 9,10-dimethoxyanthracene (DMA) as electron-donating sensitizers cooperating with 2-aryl-1,3-dimethylbenzimidazolines. BDMAP and DMP generally led higher conversion of ketones and better yield of reduction products compared to BDMAA and DMA.

2-Hydroxyphenyl-1,3-dimethylbenzimidazolines. Formal two hydrogen atom-donors for photoinduced electron transfer reactions

Both 2-(2′-hydroxyphenyl)-1,3-dimethylbenzimidazoline and 2-(4′-hydroxyphenyl)-1,3-dimethylbenzimidazoline were found to act as formal two hydrogen atom-donors for photoinduced electron transfer reactions of epoxy ketones and other carbonyl compounds.

1,3-Dimethyl-2-phenylbenzimidazoline (DMPBI)-acetic acid: An effective reagent system for photoinduced reductive transformation of α,β-epoxy ketones to β-hydroxy ketones

A combination of 1,3-dimethyl-2-phenylbenzimidazoline (DMPBI) and acetic acid has been utilized for photoinduced reductive transformation of α,β-epoxy ketones to β-hydroxy ketones. Study on photoreactions using several proton donors revealed that acetic acid is superior to other proton donors such as HCl, p-TsOH, MeOH, and water. 1,3-Dimethyl-2-phenylbenzimidazolium was produced in the reaction with acetic acid while N-benzoyl-N,N′-dimethyl-o-phenylenediamine was formed in aqueous solvents. When THF solutions containing aryl carbonyl possessing α,β-epoxy ketones and DMPBI and acetic acid were irradiated (λ > 280 nm), β-hydroxy ketones were isolated in good to excellent yields. Photosensitized conditions (λ > 340 nm) were employed for the reactions of alkyl carbonyl possessing α,β-epoxy ketones.

Lithium naphthalenide induced reductive cleavage of α,β-epoxy ketones: An efficient procedure for the preparation of β-hydroxy ketones

Lithium naphthalenide presents itself as a mild and efficient reagent for the cleavage of α,β-epoxy ketones to give the corresponding β-hydroxy ketones in good yields.

Reductive transformation of α β-epoxy ketones and other compounds promoted through photoinduced electron transfer processes with 1,3-dimethyl- 2-phenylbenzimidazoline (DMPBI)

Photoreactions of epoxy ketones, aromatic ketones, haloketones, and aromatic halides with 1,3-dimethyl-2-phenylbenzimidazoline (DMPBI) were studied. Photoinduced single-electron transfer from DMPBI to such substrates initiates the reactions, followed by radical rearrangement and reduction to finally give several reduced products in modest to good yields.

Thiol/Diselenide Exchange for the Generation of Benzeneselenolate Ion. Catalytic Reductive Ring-Opening of α,β-Epoxy Ketones

In the presence of N-acetylcysteine sodium salt, benzeneselenolate ion was generated in situ from diphenyl diselenide via thiol/diselenide and thiol/selenenyl sulfide exchange in aqueous methanol under mild conditions.Benzeneselenolate ion thus formed was efficiently alkylated and arylated to afford alkyl phenyl selenides and aryl phenyl selenides, respectively. α,β-Epoxy ketones were catalytically reduced by benzeneselenolate ion to afford β-hydroxy ketones (aldols) in good yields.The stereospecificity of the reaction was demonstrated in the preparation of optically active β-hydroxy ketones from chiral α,β-epoxy ketones.

INDIRECT ELECTROREDUCTION OF α,β-EPOXY CARBONYL COMPOUNDS AND THEIR ANALOGUES BY USE OF A (PhSe)2/SACRIFICAL ANODE SYSTEM

Indirect electroreductive transformations of α,β-epoxy carbonyl compounds 1 mediated by diphenyl diselenide ((PhSe)2) as a recyclable reagent to their β-hydroxy derivatives 2 in 80-90percent yields were achieved in an undivided cell by use of a sacrificia

Photochemically and Thermally Induced Free-Radical Reactions of α,β-Epoxy Ketones with Tributyltin Hydride: Selective Ca-O Bond Cleavage of Oxiranylmethyl Radicals Derived from α,β-Epoxy Ketones

Free-radical reactions of α,β-epoxy ketones with tributyltin hydride have been studied.These substances were selectively converted to β-hydroxy ketones under both photochemical and thermal conditions.The photoreaction is initiated by hydrogen abstraction of an epoxy ketone triplet from tributyltin hydride, while azoisobutyronitrile is used as an initiator for the thermal reaction.In general, the photoreaction conditions are particularly useful for aroyl-substituted epoxy ketones while the thermal conditions are applicable to a variety of epoxy ketones.It was also found that the epoxy esters and epoxy alcohols did not undergo the ring-opening reaction under the similar conditions.Tributyltin radical attack on the carbonyl of epoxy ketones is a key process for both the photoreaction and the thermal reaction.Regioselective ring opening of the resulting oxiranylmethyl radical finally produces β-hydroxy ketones.In order to capture the free-radical intermediates, the reaction of epoxy ketones with allyltributyltin was conducted.The isolation of α-allylated β-hydroxy ketones is interpreted by the involvement of a novel 1,5-tributyltin transfer.