Triarylamine-Substituted Benzimidazoliums as Electron Donor-Acceptor Dyad-Type Photocatalysts for Reductive Organic Transformations.

Triarylamine-substituted benzimidazoliums (BI+-PhNAr2), new electron donor-acceptor dyad molecules, were synthesized. Their photocatalytic properties for reductive organic transformations were explored using absorption and fluorescence spectroscopy, redox potential determinations, density functional theory calculations, transient absorption spectroscopy, and reduction reactions of selected substrates. The results show that irradiation of BI+-PhNAr2 promotes photoinduced intramolecular electron transfer to form a long-lived (∼300 µs) charge shifted state (BI•-PhN•+Ar2). In the pathway for photocatalysis of reduction reactions of substrates, BI•-PhN•+Ar2 is subsequently transformed to the neutral benzimidazolyl radical (BI•-PhNAr2) by single-electron transfer from the donor 1,3-dimethyl-2-phenylbenzimidazoline (BIH-Ph) serving as a cooperative agent. Among the benzimidazoliums explored, the bromo-substituted analogue BI+-PhN(C6H4Br-p)2 in conjunction with BIH-Ph demonstrates the most consistent catalytic performance.

A Photocatalytic System Composed of Benzimidazolium Aryloxide and Tetramethylpiperidine 1-Oxyl to Promote Desulfonylative α-Oxyamination Reactions of α-Sulfonylketones.

A new photocatalytic system was developed for carrying out desulfonylative α-oxyamination reactions of α-sulfonylketones in which α-ketoalkyl radicals are generated. The catalytic system is composed of benzimidazolium aryloxide betaines (BI+-ArO-), serving as visible light-absorbing electron donor photocatalysts, and 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), playing dual roles as an electron donor for catalyst recycling and a reagent to capture the generated radical intermediates. Information about the detailed nature of BI+-ArO- and the photocatalytic processes with TEMPO was gained using absorption spectroscopy, electrochemical measurements, and density functional theory calculations.

Translational isomers of N-sulfonylated [3]catenane: synthesis and isomerization.

N-Sulfonylated [3]catenanes, which exist as two translational isomers, were synthesized. The X-ray crystal structure of the distal isomer of [3]catenane, which has higher symmetry, revealed hydrogen bonds involving the carboxylic acid moieties on the terminal rings. The thermodynamic parameters of the isomerization revealed that this hydrogen bonding influenced the isomerization process.

Competitive Desulfonylative Reduction and Oxidation of α-Sulfonylketones Promoted by Photoinduced Electron Transfer with 2-Hydroxyaryl-1,3-dimethylbenzimidazolines under Air.

Desulfonylation reactions of α-sulfonylketones promoted by photoinduced electron transfer with 2-hydroxyarylbenzimidazolines (BIH-ArOH) were investigated. Under aerobic conditions, photoexcited 2-hydroxynaphthylbenzimidazoline (BIH-NapOH) promotes competitive reduction (forming alkylketones) and oxidation (producing α-hydroxyketones) of sulfonylketones through pathways involving the intermediacy of α-ketoalkyl radicals. The results of an examination of the effects of solvents, radical trapping reagents, substituents of sulfonylketones, and a variety of hydroxyaryl- and aryl-benzimidazolines (BIH-ArOH and BIH-Ar) suggest that the oxidation products are produced by dissociation of α-ketoalkyl radicals from the initially formed solvent-caged radical ion pairs followed by reaction with molecular oxygen. In addition, the observations indicate that the reduction products are generated by proton or hydrogen atom transfer in solvent-caged radical ion pairs derived from benzimidazolines and sulfonylketones. The results also suggest that arylsulfinate anions arising by carbon-sulfur bond cleavage of sulfonylketone radical anions act as reductants in the oxidation pathway to convert initially formed α-hydroperoxyketones to α-hydroxyketones. Finally, density functional theory calculations were performed to explore the structures and properties of radical ions of sulfonylketones as well as BIH-NapOH.

Sterically Regulated α-Oxygenation of α-Bromocarbonyl Compounds Promoted Using 2-Aryl-1,3-dimethylbenzimidazolines and Air.

A debrominative oxygenation protocol has been developed for the conversion of α-bromo-α,α-dialkyl-substituted carbonyl compounds to their corresponding α-hydroxy analogues. For example, stirring a solution of α-bromoisobutyrophenone and 2-aryl-1,3-dimethylbenzimidazoline (BIH-Ar) at room temperature under an air atmosphere leads to the efficient formation of α-hydroperoxyisobutyrophenone, which can be converted to α-hydroxyisobutyrophenone using Me2S reduction. In contrast, reaction of α-bromoacetophenone under the same conditions produces the α-hydrogenated product acetophenone. α-Keto-alkyl and benzimidazolyl radicals (BI•-Ar), generated via dissociative electron transfer from BIH-Ar to α-bromoketone substrates, serve as key intermediates in the oxidation and reduction processes. The dramatic switch from hydrogenation to oxygenation is attributed to a steric effect of α-alkyl substituents, which causes hydrogen atom abstraction from sterically crowded BIH-Ar to α-keto-alkyl radicals to be slow and enable preferential reaction with molecular oxygen. Generation of the α-keto-alkyl radical and BI•-Ar intermediates in these process and their sterically governed hydrogen atom transfer reactions are supported by results arising from DFT calculations. Moreover, an electron spin resonance study showed that visible light irradiation of phenyl benzimidazoline (BIH-Ph) in the presence of molecular oxygen produces the benzimidazolyl radical (BI•-Ph). The addition of thiophenol into the reaction of α-bromoisobutyrophenone and BIH-Ph predominantly produced α-phenylthiolated isobutyrophenone even if a high concentration of molecular oxygen exists. Furthermore, the developed protocol was applied to other α-bromo-α,α-dialkylated carbonyl compounds.

Protocol for Visible-Light-Promoted Desulfonylation Reactions Utilizing Catalytic Benzimidazolium Aryloxide Betaines and Stoichiometric Hydride Donor Reagents.

An unprecedented photocatalytic system consisting of benzimidazolium aryloxide betaines (BI+-ArO-) and stoichiometric hydride reducing reagents was developed for carrying out desulfonylation reactions of N-sulfonyl-indoles, -amides, and -amines, and α-sulfonyl ketones. Measurements of absorption spectra and cyclic voltammograms as well as density functional theory (DFT) calculations were carried out to gain mechanistic information. In the catalytic system, visible-light-activated benzimidazoline aryloxides (BIH-ArO-), generated in situ by hydride reduction of the corresponding betaines BI+-ArO-, donate both an electron and a hydrogen atom to the substrates. A modified protocol was also developed so that a catalytic quantity of more easily prepared hydroxyaryl benzimidazolines (BIH-ArOH) is used along with a stoichiometric hydride donor to promote the photochemical desulfonylation reactions.

Visible Light and Hydroxynaphthylbenzimidazoline Promoted Transition-Metal-Catalyst-Free Desulfonylation of N-Sulfonylamides and N-Sulfonylamines.

A visible light promoted process for desulfonylation of N-sulfonylamides and -amines has been developed, in which 1,3-dimethyl-2-hydroxynaphthylbenzimidazoline (HONap-BIH) serves as a light absorbing, electron and hydrogen atom donor, and a household white light-emitting diode serves as a light source. The process transforms various N-sulfonylamide and -amine substrates to desulfonylated products in moderate to excellent yields. The observation that the fluorescence of 1-methyl-2-naphthoxy anion is efficiently quenched by the substrates suggests that the mechanism for the photoinduced desulfonylation reaction begins with photoexcitation of the naphthoxide chromophore in HONap-BIH, which generates an excited species via intramolecular proton transfer between the HONap and BIH moieties. This process triggers single electron transfer to the substrate, which promotes loss of the sulfonyl group to form the free amide or amine. The results of studies employing radical probe substrates as well as DFT calculations suggest that selective nitrogen-sulfur bond cleavage of the substrate radical anion generates either a pair of an amide or amine anion and a sulfonyl radical or that of an amidyl or aminyl radical and sulfinate anion, depending on the nature of the N-substituent on the substrate. An intermolecular version of this protocol, in which 1-methyl-2-naphthol and 1,3-dimethyl-2-phenylbenzimidazoline are used concomitantly, was also examined.

Benzimidazolium Naphthoxide Betaine Is a Visible Light Promoted Organic Photoredox Catalyst.

Benzimidazolium naphthoxide (-ONap-BI+) was first synthesized and utilized as an unprecedented betaine photoredox catalyst. Photoexcited state of -ONap-BI+ generated by visible light irradiation catalyzes the reductive deiodination as well as desulfonylation reactions in which 1,3-dimethyl-2-phenylbenzimidazoline (Ph-BIH) cooperates with as an electron and hydrogen atom donor. Significant solvent effects on the reaction progress were discovered, and specific solvation toward imidazolium and naphthoxide moieties of -ONap-BI+ was proposed.

Solvent-Dependent Reaction Pathways Operating in Copper(II) Tetrafluoroborate Promoted Oxidative Ring-Opening Reactions of Cyclopropyl Silyl Ethers.

Oxidative ring-opening reactions of benzene-fused bicyclic cyclopropyl silyl ethers, promoted by copper(II) tetrafluoroborate, were investigated. The regioselectivity of cyclopropane ring-opening as well as product distributions were found to be highly dependent on the nature of the solvent. In alcohols, dimeric substances arising from external bond cleavage are major products. Radical rearrangement products are also formed in solvents such as ether and ethyl acetate. On the contrary, nucleophile addition to carbocation intermediates, generated by internal bond cleavage, occurs mainly in reactions taking place in acetonitrile. It is proposed that the observed solvent effects that govern the reaction pathways followed are a consequence of varying solvation of copper intermediates, which governs their reactivity and redox properties. In addition, the influence of counteranions of the copper salts, organonitriles, cyclic dienes, and substrate structures on the pathways followed in these reactions was also examined.

Synthesis of linear [5]catenanes via olefin metathesis dimerization of pseudorotaxanes composed of a [2]catenane and a secondary ammonium salt.

[5]Catenanes were synthesized by olefin metathesis dimerization. The reaction of pseudorotaxanes, which were derived from a [2]catenane and one equivalent of an ammonium salt bearing two terminal olefins in dichloromethane, with a catalytic amount of Grubbs catalyst afforded linear [5]catenanes in 12% yield. Intermolecular and intramolecular olefin metathesis reactions were controlled by the length of the alkyl chain of the ammonium salts.

Metal-free, one-pot, sequential protocol for transforming α,ß-epoxy ketones to ß-hydroxy ketones and α-methylene ketones.

A new sequential, one-pot protocol for transforming 1,3-disubstituted 2,3-epoxy ketones to ß-hydroxy ketones and α-methylene ketones has been developed. Reaction of epoxy ketones with boron trifluoride etherate (BF3·OEt2) generates the cationic intermediates by regioselective epoxide ring opening and an acyl shift. Then, a treatment of these cations with 2-aryl-1,3-dimethylbenzimidazolines (DMBIH) results in formation of 1,2-disubstituted 3-hydroxy ketones. DMBIH serves as a hydride donor in the second step of this process. Finally, the ß-hydroxy ketones can be converted to 1,2-disubstituted 2-methylene ketones by treatment with methanesulfonic acid or a combination of methanesulfonyl chloride and triethylamine. Importantly, the sequential steps involved in formation of the α-methylene ketone products can be carried out in one pot.

Double axial chirality promoted asymmetric [2,3] Stevens rearrangement of N-cinnamyl L-alanine amide-derived ammonium ylides.

The base-induced asymmetric [2,3] Stevens rearrangement of N-cinnamyl tetraalkylammonium ylides derived from L-alanine amides proceeds via a double axially chiral intermediate to afford the corresponding α-substituted alanine derivatives with high enantio- and diastereoselectivities.

Copper(II)-salt-promoted oxidative ring-opening reactions of bicyclic cyclopropanol derivatives via radical pathways.

Copper(II)-salt-promoted oxidative ring-opening reactions of bicyclic cyclopropanol derivatives were investigated. The regioselectivities of these processes were found to be influenced by the structure of cyclopropanols as well as the counter anion of the copper(II) salts. A mechanism involving rearrangement reactions of radical intermediates and their competitive trapping by copper ions is proposed.

Selective synthesis of [2]- and [3]catenane tuned by ring size and concentration.

The syntheses of [2]- and [3]catenanes by olefin metathesis and oxidative acetylide coupling have been studied in detail. Pseudorotaxanes that were obtained by mixing crown ether and ammonium salts containing two terminal reactive end-groups were converted to [2]- and [3]catenane. Their yields were influenced not only by the chain length of the ammonium salts but also by the concentration of the crown ether and the ammonium salts. The strain energies of [2]catenane were responsible for the formation of [2]catenane.

Asymmetric α-2-tosylethenylation of N,N-dialkyl-L-amino acid esters via the formation of non-racemic ammonium enolates.

Asymmetric α-2-tosylethenylation of (S)-2-(pyrrolidin-1-yl)propanoic acid esters was shown to produce good yields with high enantioselectivities. The reaction proceeds via the formation of a non-racemic ammonium enolate without an external source of chirality.

Highly shape-selective guest encapsulation in the precisely defined cavity of a calix[4]arene-capped metalloporphyrin.

We developed a metalloporphyrin-based molecular container capped with a calix[4]arene, and its rigid cavity distinguished the slight structural differences in the aromatic guests.