A regioselective approach toward the synthesis of pharmacologically important quinone-containing heterocyclic systems

An inexpensive and regioselective approach to dihydrothieno[3,2-g]quinoline-4,9-dione is reported. A combination of a mild version of Skraup reaction with a sequential substitution/Michael addition allowed the selective preparation in acceptable yield of a pharmacologically important quinone derivative, previously obtained only in trace and together with the other regioisomer.     

Dipeptides containing D-serine or D-isoserine from the same (R)-aziridine-2-imide by a simple reversal of the synthetic procedure

The ring expansion of 3-unsubstituted (R)-aziridine-2-imide-containing dipeptide under acidic conditions gives rise to oxazoline-5-imide regio and stereoselectively, which can be hydrolysed to the dipeptide containing D-isoserine. On the other hand, the ring opening of 3-unsubstituted (R)-aziridine-2-ester dipeptide, easily obtained from the same (R)-aziridine, gives the regioisomeric dipeptide containing D-serine.     

A new synthesis of 2,2′-dialkylchrom-3-enes and flav-3-enes

N-iodosuccinimide (NIS) induces cyclization of substituted 2-allyl-phenols to 3-iodochromanes which may be dehydrohalogenated to the corresponding chrom-3-enes.     

Synthesis of chiral non-racemic intermediates and Arg-Gly-Asp mimetics by CaLB-catalyzed resolution

The reactivity of both the ester and amine functions present in β-amino esters was tested in order to obtain the synthesis of enantiopure αvβ3 and α5β1 integrin ligands. CaLB successfully catalyzed both the enantioselective transesterification and the N-acylation of racemic β-amino esters, allowing the isolation of intermediates for the preparation of Arg-Gly-Asp (RGD) mimetic compounds. In particular, a CaLB-catalyzed amidation reaction with unprotected p-aminobenzylamine reduced the number of synthetic steps, thus avoiding protection and deprotection of the intermediate compounds. Following this procedure, RGD mimetics were isolated with high yields and enantiomeric purities.     

Revisiting the thermal decomposition of five <Emphasis Type="Italic">ortho</Emphasis>-substituted phenyl azides by calorimetric techniques

The thermal decomposition (TD) of 2-azidophenylmethanol (1), 2-azidobenzenecarbaldehyde (2), 1-(2-azidophenyl)-1-ethanone (3), (2-azidophenyl)(phenyl)methanone (4) and 1-azido-2-nitrobenzene (5) was analysed by DSC, TG and C80 calorimetric techniques under both oxidative and non-oxidative conditions. The TD of these azides in solution is well known to give the corresponding benzoxazoles, generally in good yields, with the exception of azide 1. When both the outcomes from the solid phase and in ‘solution phase’ TD reactions combined with the results from EI-MS experiments were considered, sufficient information was available to estimate the azides intrinsic molecular reactivity (MIR).     

The relative roles of vowels and consonants in discriminating talker identity versus word meaning

Three experiments tested the hypothesis that vowels play a disproportionate role in hearing talker identity, while consonants are more important in perceiving word meaning. In each study, listeners heard 128 stimuli consisting of two different words. Stimuli were balanced for same/different meaning, same/different talker, and male/female talker. The first word in each was intact, while the second was either intact (Experiment 1), or had vowels ("Consonants-Only") or consonants wels-Only") replaced by silence (Experiments 2, 3). Different listeners performed a same/ different judgment of either talker identity (Talker) or word meaning (Meaning). Baseline testing in Experiment 1 showed above-chance performance in both, with greater accuracy for Meaning. In Experiment 2, Talker identity was more accurately judged from Vowels-Only stimuli, with modestly better overall Meaning performance with Consonants-Only stimuli. However, performance with vowel-initial Vowels-Only stimuli in particular was most accurate of all. Editing Vowels-Only stimuli further in Experiment 3 had no effect on Talker discrimination, while dramatically reducing accuracy in the Meaning condition, including both vowel-initial and consonant-initial Vowels-Only stimuli. Overall, results confirmed a priori predictions, but are largely inconsistent with recent tests of vowels and consonants in sentence comprehension. These discrepancies and possible implications for the evolutionary origins of speech are discussed.     

Highly regio- and stereoselective palladium-catalyzed allylic carbonate amination. A practical route to dehydro-β-amino esters

A pratical, highly enantioselective method for the synthesis of dehydro-β-amino acids was developed starting from easily accessible enantiopure allylic carbonates. The substitution with amines for C–N bond formation on these substrates bearing substituents on the Cα, Cβ, and Cγ position of the allylic system has received, until now, little attention. The reactions, carried out under palladium-catalyzed conditions, resulted in good yields and complete regioselectivity. Moreover, starting from enantiopure carbonates, complete retention of the configuration could be observed, affording enantiopure allylic amines.     

Tunable infrared generation in KTA and applications

Noncollinear difference frequency mixing of dye laser and Nd:YAG second harmonic (fundamental) radiation from a commercial laser system is employed for the generation of 2.7–5.3 μm (1.6–1.7 μm) radiations in a flux-grown KTiOAsO₁ crystal. The generated radiation is used to scan the methane absorption in the fundamental (v ₃) and its first overtone (2v ₃) band at pressure 90 torr in a laboratory made single pass gas cell of length 33 cm.