Direct Oxidation of N‐Benzylamides to Aldehydes or Ketones by N‐Bromosuccinimide

A simple and efficient approach for the one‐pot transformation of N‐benzylamides to aldehydes or ketones under mild conditions was reported. All the 20 substrates gave moderate to excellent oxidative yields under the optimized conditions. Our study may provide a new approach for the one‐pot synthesis of aldehydes or ketones from the corresponding amides.     

Synthesis of novel chiral phosphines from α,α-trehalose

New disaccharide chiral phosphines, such as 4,6-O-benzylidene-2-(diphenylphosphino)-2-deoxy-α-d-altropyranosyl-(1,1)-4,6-O-benzylidene-2-(diphenylphosphino)-2-deoxy-α-d-altropyranoside 1 and 2-(diphenylphosphino)-2-deoxy-4,6-O-isopropylidene-α-d-altropyranosyl-(1,1)-2-(diphenylphosphino)-2-deoxy-4,6-O-isopropylidene-α-d-altropyranoside 9, were prepared from α,α-trehalose. We also succeeded in the synthesis of polyhydroxy chiral diphosphine 2-(diphenylphosphino)-2-deoxy-α-d-altropyranosyl-(1,1)-2-(diphenylphosphino)-2-deoxy-α-d-altropyranoside 5 by deprotection of isopropylidene groups.     

Enantioselective Michael addition of α,α-disubstituted aldehydes to maleimides organocatalyzed by chiral primary amine-guanidines

New primary amine-guanidines derived from the monoguanylation of (1S,2S)- and (1R,2R)-cyclohexane-1,2-diamine have been prepared and used as chiral organocatalysts for the enantioselective conjugate addition of α,α-disubstituted aldehydes to maleimides. The corresponding Michael adducts bearing a new stereocenter were generally obtained in high or quantitative yields and with good enantioselectivities (up to 93% ee).     

Microbial Oxidation of (-)-α-pinene to Verbenol Production by Newly Isolated Strains

Verbenol is a bicyclicbicycle secondary allylic alcohol, with pronounced camphor and mint flavor notes, mainly used as food flavoring. This compound is also used to control harmful insects, and hence has potential for using in agriculture, and is an intermediate in the synthesis of valuable perfume and medicinal substances. This work is focused on the microbial oxidation of (-)-α-pinene to verbenol production. To carry out the present study, 405 microorganisms were tested for their ability to bioconvert the substrate. From the isolated microorganisms, 193 were selected in the pre-screening using mineral medium for limonene degradation. At the screening step, 31 strains were able to convert (-)-α-pinene in verbenol. The highest concentration in verbenol from (-)-α-pinene was about 125.6 mg/L for yeast isolated from orange juice industrial residue.     

Synthesis of novel chiral lipophilic pyridyl-containing β-amino alcohol ligands and enantioselective hydrolysis of α-amino acid esters by chiral metallomicelles

Seven novel chiral lipophilic pyridyl-containing β-amino alcohol ligands have been synthesized by coupling of 6-alkoxymethyl-2-chloromethylpyridine 3 with the corresponding chiral β-amino alcohols or l-cysteine. Their metal ion complexes have been investigated as catalysts for the enantioselective hydrolysis of N-protected α-amino acid esters in aqueous comicellar solution. The results indicate that the hydrophobic interactions between substrate and metallocatalyst, the rigidity of the ligand, the hydroxyl group of the ligand acting as a nucleophile for the transacylation process, and the micellar microenvironment are important factors for the activity and enantioselectivity. Large rate accelerations (up to three orders of magnitude) and moderate enantioselectivities (up to 7.81 (k_R/k_S)) employing 4a–Cu²⁺ have been observed.     

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.     

Efficient Procedure for Oxidation of Benzylic Alcohols to Carbonyl Compounds by N‐Bromosuccinimide in Ionic Liquid

Abstract

Efficient oxidation of various benzylic alcohols to the corresponding carbonyl compounds has been achieved in the presence of NBS and 2,6‐lutidine in ionic liquid [bmim]BF₄.     

Synthesis of chiral dihydrofuran compounds by thiourea derivatives-catalyzed“interrupted”Feist-Bénary reaction

<正>In this study,six thiourea derivatives of cinchona alkaloids with 9-nat or 9-epi-configuration were synthesized.After characterized the structures,we adopted them to the asymmetric"interrupted"Feist-Benary(IFB) reaction ofα-haloketones with β-dicarbonyl compounds,to give optically active dihydrofurans.Various thiourea derivatives as organocatalysts were examined.The corresponding chiral hydroxyl dihydrofurans have been obtained in excellent yields and moderate ees.To the acyclic substrate,we obtained exciting and promising result.     

Synthesis of chiral α-ethylphenylamine salts of tartaric acid and novel application to cyanosilylation of prochiral ketones

Abstract  

Chiral α-ethylphenylamine tartaric acid salts were synthesized from α-ethylphenylamine by direct reaction with chiral tartaric acid. The crystal structure of S-(−)-α-ethylphenylamine-(2R,3R)-(−)-dihydroxybutanedioic acid was determined. The crystal is monoclinic, of space group P2_1/n , with a = 6.331(5) ?, b = 14.209(11) ?, c = 7.495(6) ?, α = 90.00o, β = 107.000(13)o, γ = 90.00o, λ = 0.7103 Ǻ, V = 644.7(9), Z = 2, D _c = 1.397 g/cm³, M _r  = 271.27 and F(000) = 288, R = 0.0477, and ωR = 0.0838 for 1388 observed reflections with I > 2σ(I). We then used the chiral α-ethylphenylamine tartaric acid salts as catalysts in the cyanosilylation of prochiral ketones, and moderate conversions were obtained.     

Diastereoselective and enantioselective capture of chiral zinc enolate using nitroolefins: a rapid access to chiral γ-nitro carbonyl compounds

Highly diastereoselective and enantioselective catalytic capture of chiral zinc enolates using nitroolefins as electrophiles is described. The tandem products γ-nitro ketones were obtained in good yields with high diastereoselectivities and enantioselectivities. The γ-nitro ketones were readily hydrogenated to the optically enriched and diastereomerically pure chiral pyrrolidines with four contiguous stereocentres under mild conditions.     

Synthesis of chiral cyclic nitrones by asymmetric addition of β-ketosulfones to nitroalkenes followed by reductive cyclization

The first organocatalytic addition of β-ketosulfones to nitroalkenes catalyzed by thiourea cinchona alkaloids is presented. The readily obtained addition products were selectively transformed into chiral nitrones by reduction of the nitro group and in situ cyclization (up to 99:1 e.r. and >98:2 d.r.). Moreover, the utility of this method has additionally been demonstrated by the further transformation to functionalized N-hydroxypyrrolidines that possess a quaternary center by addition of trimethylsilyl cyanide (TMSCN) to the C=N bond of the cyclic nitrones in the presence of a Lewis acid.     

Synthesis of novel chiral phosphine-triazine ligand derived fromα-phenylethylamine for Pd-catalyzed asymmetric allylic alkylation

A novel chiral phosphine-triazine ligand was synthesized from chiralα-phenylethylamine through a three-step procedure.In a model reaction of Pd-catalyzed allylic alkylation of rac-1,3-diphenylprop-2-en-l-yl pivalate with dimethyl malonate,good enantioselectivity (90% e.e.) was obtained by using this ligand.     

An aziridine route to chiral β-lactams a novel entry to (+)-thienamycin

Enantiomerically pure 2,3- epoxy alcohols are transformed readily and stereospecifically to the corresponding aziridines, regioselective ring-opening of which allows subsequent conversion to chiral β-lactams suitable for elaboration to the title antibiotic.     

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.     

Highly asymmetric Michael additions of α,α-disubstituted aldehydes to β-nitroalkenes promoted by chiral pyrrolidine-thiourea bifunctional catalysts

A series of secondary amine-thiourea catalysts derived from l-proline and chiral diamine were prepared and first applied to the Michael addition of α,α-disubstituted aldehydes to trans-β-nitroalkenes. Moderate yields (47-75%) and excellent enantioselectivities (up to 96% ee) were obtained for a variety of aryl and heteroaryl nitroalkenes.     

Addition of α,α-dichloropropionitrile to unsaturated compounds under conditions of metallocomplex initiation

,-Dichloropropionitrile reacts with unsaturated compounds in the presence of complex initiating systems based on metal carbonyls. The systems based on iron pentacarbonyl are the most efficient.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1595–1596, August, 1995.The work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-04497).