Silver (I)-promoted asymmetric halohydrin reaction of chiral N-enoyl-2-oxazolidinones: scope and limitations

The halohydrin reaction of chiral N-enoyl-2-oxazolidinones 1 by halogen (Br₂/I₂) and water were efficiently carried out in aqueous organic solvent promoted by silver(I) with high anti- and regioselectivity and moderate to good diastereoselectivities. The alkenoyl, cinnamoyl and electron-deficient cinnamoyl substrates smoothly underwent bromohydrin reaction in aqueous acetone but no iodohydrin reaction, where as electron-rich cinnamoyl substrates preferred to undergo iodohydrin reaction in aqueous acetone with moderate diastereoselectivity and enhanced diastereoselectivity was observed in aqueous THF.     

Remote Raman and fluorescence studies of mineral samples

In the present study, we investigated remote laser-induced fluorescence (LIF), at a distance of 4.8 m, of a variety of natural minerals and rocks, and Hawaiian Ti (Cordyline terminalis) plant leaves. These minerals included calcite cleavage, calcite onex and calcite travertine, gypsum, fluorapatite, Dover flint and chalk, chalcedony and nephelene syenite, and rubies containing rock. Pulsed laser excitation of the samples at 355 and 266 nm often resulted in strong fluorescence. The LIF bands in the violet-blue region at approximately 413 and approximately 437 nm were observed only in the spectrum of calcite cleavage. The green LIF bands with band maxima in the narrow range of approximately 501-504 nm were observed in the spectra of all the minerals with the exception of the nephelene syenite and ruby rocks. The LIF red bands were observed in the range approximately 685-711 nm in all samples. Excitation with 532 nm wavelength laser gave broad but relatively low fluorescence background in the low-frequency region of the Raman spectra of these minerals. One microsecond signal gating was effective in removing nearly all background fluorescence (with peak at approximately 610 nm) from calcite cleavage Raman spectra, indicating that the fluorescence was probably from long-lifetime inorganic phosphorescence.     

Stereoselective syntheses of (−)-chloramphenicol and (+)-thiamphenicol

Chloramphenicol and thiamphenicol have been enantioselectively synthesized using an asymmetric halohydrin reaction as a key step. In particular, halomethoxylation reaction was used, where O-methyl functions as a hydroxyl protecting group and eliminates an additional protection step.     

Pulsed remote Raman system for daytime measurements of mineral spectra

A remote Raman system has been developed utilizing a 532nm pulsed laser and gated intensified charged couple device (ICCD) detector in the oblique geometry. When the system is set for 50m sample distance it is capable of measuring Raman spectra of minerals located at distances in the range of 10-65m from the telescope. Both daytime and nighttime operations are feasible and the spectra of minerals can be measured in a short period of time, of the order of a few seconds. In oblique geometry, measured sampling depth is more than 30m, during which the system maintains very high performance without any adjustments. Much longer sampling depth (0.1-120m) has been observed when the system is configured in the coaxial geometry. Clear advantages of using a gated detection mode over the continuous (CW) mode of operation in reducing the background signal and eliminating long-lived fluorescence signals from the Raman spectra are presented. The performance of the pulsed Raman system is demonstrated by measuring spectra of Raman standards including benzene (C(6)H(6)) and naphthalene (C(10)H(8)), a low Raman cross section silicate mineral muscovite (KAl(2)(Si(3)Al)O(10)(OH)(2)), and a medium Raman cross section mineral calcite (CaCO(3)).     

Autofluorescence characterization of advanced glycation end products of hemoglobin

This article describes the analysis of autofluorescence of advanced glycation end products of hemoglobin (Hb-AGE). Formed as a result of slow, spontaneous and non-enzymatic glycation reactions, Hb-AGE possesses a characteristic autofluorescence at 308/345 nm (lambda(ex)/lambda(em)). Even in the presence of heme as a quenching molecule, the surface presence of the glycated adduct gave rise to autofluorescence with the quantum yield of 0.19. The specificity of monoclonal antibody developed against common AGE structure with Hb-AGE was demonstrated using reduction in fluorescence polarization value due to increased molecular volume while binding. The formation of fluorescent adduct in hemoglobin in the advanced stage of glycation and the non-fluorescent HbA(1c) will be of major use in distinguishing and to know the past status of diabetes mellitus. While autofluorescence correlated highly with HbA(1c) value under in vivo condition (r = 0.85), it was moderate in the clinical samples (r = 0.55). The results suggest a non-linear relation between glycemia and glycation, indicating the application of Hb-AGE as a measure of susceptibility to glycation rather than glycation itself.     

Microwave Assisted Rupture of Furoxans to Nitrile Oxides and Intermolecular Capture by Dipolarophiles

3,4-Diaroylfuroxans 1 react with various dipolarophiles 3 under microwave activation to afford the cycloadduct 4 instead of the expected isoxazole 5 in good yields in the absence of solvent.     

Application of Polyphosphoric Acid‐Mediated Acyl Migration for Regiospecific Synthesis of Diverse 2‐Acylpyrroles from Chalcones

A metal‐free approach for the synthesis of 2‐acylpyrroles is reported in this paper. Synthesis of the target molecule started from chalcones and was carried out in two steps. Initial step involved the conversion of chalcones to corresponding 4‐substituted‐3‐acylpyrroles by reaction with TosMIC. In the subsequent step, target molecules were obtained in modest to good yields by polyphosphoric acid‐mediated acyl rearrangement of 3‐acylpyrroles to their 2‐acyl congeners. The crucial final step was amenable to diverse substitutions on pyrrole ring. Preliminary experiment for the determination of mechanism indicated the involvement of acylium ion.