Synthesis of α-functional nitro compounds by the nitration of activated carbonyl compounds in a two-phase system

2-Nitro-1,3-dicarbonyl and -nitromonocarbonyl compounds were synthesized in the yields varying from moderate (30 %) to nearly quantitative by the nitration of -dicarbonyl compounds in a two-phase system: sulfuric/nitric acid mixture-chloroform at - 10÷10 °C. The use of phase transfer conditions made it possible to avoid the formation of furoxans as by-products and to simplify the isolation of products. This method is quite common for preparing various -functional nitro compounds including those containing a CF₃-group. Key words: nitration, -functional nitro compounds.Translated fromIzvestiya Akademn Nauk. Seriya Khimicheskaya, No. 1, pp. 76–79, January, 1994.     

Sulfoxide-mediated α-arylation of carbonyl compounds

A novel sulfoxide-mediated α-arylation of carbonyl compounds is reported. This reaction proceeds under very mild conditions at room temperature and does not require any transition-metal promoter or catalyst.     

Synthesis of 3-acylated indoles through iron-catalyzed oxidative coupling of indoles with α-amino carbonyl compounds

A novel iron-catalyzed oxidative coupling of indoles with α-amino carbonyl compounds has been developed. The transformation provides an attractive approach to the synthesis of 3-acylindoles, with the advantages of easily available starting materials and high functional group tolerance. Furthermore, control experiments imply that a radical process maybe involved in this reaction.     

Aerobic photo-decarboxylation of α-hydroxy carboxylic acid derivatives under visible light irradiation in the presence of catalytic iodine

A catalytic amount of iodine enables us to carry out aerobic photo-decarboxylation of α-hydroxy carboxylic acid derivatives to the corresponding carboxylic acids or ketones selectively in high yields under irradiation of vis. This new oxidation is interesting in keeping with the notion of Green Chemistry due to the non-use of heavy metals and halogenated solvents, waste reduction, and the use of molecular oxygen.     

Insertion of cyclopropanes between a carbonyl carbon and an α-carbon of carbonyl compounds with cyclopropylmagnesium carbenoids

The reaction of the lithium enolates of α-aryl carbonyl compounds with cyclopropylmagnesium carbenoids, derived from 1-chlorocyclopropyl p-tolyl sulfoxides with i-PrMgCl at low temperature, resulted in the formation of β-aryl carbonyl compounds bearing a cyclopropane ring at the α-position with one-carbon homologation in variable yields. The reaction was found to be highly stereospecific with respect to the stereochemistry of the cyclopropylmagnesium carbenoids. Mechanism and origin of the stereospecificity of the reaction are also discussed. This is the first example for the insertion of cyclopropanes in between a carbonyl carbon and an α-carbon of carbonyl compounds.     

A novel olefination of carbonyl compounds with α-bromoacetic ester mediated by tri-n-butylstibine

Tri-n-butylstibine has been found to mediate the olefinatlon of carbonyl compounds by α-bromoacetic ester to give corresponding olefins in good yields.     

Selective hydrogenation of α,β-unsaturated carbonyl compounds by rhodium trichloride and aliquat®-336 in a two-phase liquid system

The solvated ion pair [(C₈H₁₇)₃NCH₃]⁺[RhCl₄]⁻, formed from aqueous rhodium trichloride and Aliquat^®-336 in a two-phase liquid system, was shown to hydrogenate α,β-unsaturated ketones and esters selectively at the C-C double bonds. The reduction of benzylideneacetophenone was found to follow first-order kinetics in the substrate only below 0.2 M, and to approach second-order in H₂; at partial pressures of < 0.12 atm. The catalysis also proved to depend on the nature of the solvent, the phase transfer catalyst and the stirring rate. The observed activation energy E_a = 12.4 kcal mol⁻¹ suggests that the process is both chemically and diffusion controlled.     

α-Fluoroalkylation of carbonyl compounds mediated by a highly reactive alkyl-rhodium complex

Treatment of silyl enol ethers of various carbonyl compounds with Et₂Zn and fluoroalkyl halides (R_f-X) in the presence of RhCl(PPh₃)₃ in DME gave the corresponding α-R_f carbonyl compounds. A highly reactive alkyl-rhodium complex which was derived from RhCl(PPh₃)₃ and Et₂Zn must be crucial in this reaction by accelerating the reaction rate and improving the yields dramatically. This reaction overcomes difficulties on the synthesis of α-R_f carbonyl compounds due to inverse polarization of R_f-X.     

ChromiumVI oxide −70% tert.butyl hydroperoxide,a simple catalytic system for oxidation of alcohols to carbonyl compounds

Oxidation of alcohols to carbonyl compounds was carried out by using catalytic amounts of CrO₃ and excess of aqueous t.BuOOH. This system is highly efficient in the case of secondary benzylic alcohols. A catalytic cycle which retains the initial oxidation state of chromium is proposed.     

Selective α-bromination of aryl carbonyl compounds: prospects and challenges

The α-bromination of carbonyl compounds is one of the most important transformations and also important precursors in synthetic organic chemistry. Particularly, the side chain monobromination of carbonyl compounds has been a challenging task, because during the reaction a small amount of disubstituted or ring brominated products as an impurity is always accompanied with monosubstituted product in the reaction mixture. In recent years substantial advances have been made for the synthesis of brominated aromatic carbonyl compounds with high selectivity. In this review, we have summarized various methods for the synthesis of α-bromo aromatic carbonyl compounds.     

Polymerisation of dithiocarbamates by oxidative coupling using iodine as oxidant—I. Synthesis and characterisation

A novel polymer has been synthesised by reacting hexamethylene diamine with carbon disulphide by the oxidative coupling method using iodine as oxidant. The first step of the polymerisation involves the formation of dithiocarbamate by reacting a diamine with carbon disulphide in alkaline medium at low temperature (5–10°) in a protic solvent such as alcohol or water. Next, the dithiocarbamate is coupled with a diamine using iodine as the oxidant at ambient temperature. The polymerisation proceeds by a radical mechanism. The molecular weight of the polymer is not very high (∼ 12,000); it is soluble in polar solvents. It was characterised by elemental analysis (N, S) and i.r. and NMR spectroscopy. The physical characteristics have been studied.     

Trifluoromethyl group induced highly stereoselective synthesis of α-hydroxy carbonyl compounds

The reaction of enolate prepared from ethyl 3-methyl-4,4,4-tri-fluorobutyrate with MoO₅-Py-HMPA complex provides ethyl (2S,3S)-2-hydroxy-3-methyl-4,4,4-trifluorobutyrate predominantly. In contrast, NaBH₄ reduction of the corresponding 2-oxobutyrate affords (2R, 3S)-hydroxyester preferentially.     

A convenient catalytic oxidative 1,2-shift of arylalkenes for preparation of α-aryl ketones mediated by NaI

Using a catalytic amount of Nal and a stoichiometric oxidant Oxone~@,a convenient procedure has been developed for the catalytic oxidative 1,2-shift of arylalkenes in CH_3CN/H_2O at room temperature,which provides the corresponding α-aryl ketones in moderate to good yields.In this protocol,sodium iodide is first oxidized into hypoiodous acid,which reacts with arylalkene to afford iodohydrin.Then,the iodohydrin is transformed into the α-aryl ketone via an oxidative 1,2-shift rearrangement.     

Lead(IV) acetate oxidative ring-opening of 2,3-epoxy primary alcohols: a new entry to optically active α-hydroxy carbonyl compounds

The treatment of 2,3-epoxy primary alcohols with lead(IV) acetate (LTA) leads to α-acetoxy aldehydes or α-acetoxy ketones, through the nucleophilic ring-opening of an intermediate oxonium and the subsequent carbon-carbon bond cleavage. This reaction represents a new route to optically active α-hydroxy carbonyl compounds.     

Copper-catalyzed β-boration of α,β-unsaturated carbonyl compounds with tetrahydroxydiborane

The copper-catalyzed β-boration of α,β-unsaturated carbonyl compounds with tetrahydroxydiborane has been developed. This diboron reagent allows direct, efficient access to boronic acids and their derivatives. Primary, secondary, and tertiary α,β-unsaturated amides are converted to the corresponding β-trifluoroboratoamides in good to excellent yields. The β-boration of a variety of α,β-unsaturated esters and ketones is also reported.     

New one-pot synthesis of pyrazole-5-carboxylates by 1,3-dipole cycloadditions of ethyl diazoacetate with α-methylene carbonyl compounds

A facile one-pot procedure for the synthesis of pyrazole-5-carboxylates by 1,3-dipolar cycloaddition of ethyl diazoacetate is described. Cycloadditions with α-methylene carbonyl compounds utilizing 1,8-diazabicyclo[5.4.0]undec-7-ene as base and acetonitrile as solvent provide pyrazoles with excellent regioselectivity and good yields. The reaction was found to proceed by a domino 1,3-dipolar cycloaddition-water elimination.     

The silapinacol rearrangement: Conversion of α,β-dihydroxysilanes into α-silyl carbonyl compounds

Treatment of α,β-dihydroxysilanes with trifluoroacetic acid in chloroform results in a 1,2-migration of the silyl group to give α-silyl aldehydes and ketones. The t-butyldimethylsilyl compounds can be isolated in high yields.