On the Way to α-Methyl-α-amino Acids; Unusual Elimination-addition in 3,3-Disubstituted 1,4-Benzodiazepin-2-ones and Inversion of Enantioselectivity in the Lipase Catalyzed Acetylation

(−)-3 -Methanesulfoxymethyl-3-acetoxoymethyl-7-chloro-5-phenyl-1,4-benzodiazepin-2-one, (−)-2, reacts with ethanethiol in the presence of a strong base affording racemic elimination-addition product 3-ethylthiomethyl-7-chloro-5-phenyl-1,4-benzodiazepin-2-one (4). In-termediary 3-methylene-7-chloro-5-phenyl-1,4-benzodiazepin-2-one (3) is formed by pericyclic C−C bond breaking during elimination of both acyloxy groups. The second approach to α-methyl-α-amino acids comprises kinetic resolution of racemic 3-hydroxymethyl-3-benzyl-7-chloro-5-phenyl-1,4-benzodiazepin-2-one (7) via acetylation by Novozym 435 lipase; enantiomeric excess (e.e.) for alcohol (3S)-(+)-7 33.2%; e.e. for acetate (3R)-(−)-8 30.2%. Opposite direction of enantio-selectivity during acetylation of 7 and the recently studied 9 (Ref. 3) was established by determination of absolute conformation and rela-tive configuration at C(3) (pseudoaxial/pseudoequatorial) by com-bining CD and 1H NMR spectroscopy

HRVATSKO KEMIJSKO DRUŠTVO Zapisnik redovite godišnje skupštine 1999

Redovita Godišnja skupština Hrvatskog kemijskog društva održana je u petak, 10. prosinca 1999. godine u predavaonici Zavoda za organsku kemiju Prirodoslovno-matematičkog fakulteta Sveučilišta u Zagrebu, Trg J. J. Strossmayera 14, Zagreb

Local characteristics of the standing genetic diversity of European beech with high within-region differentiation at the eastern part of the range

Developing "climate smart forestry" (CSF) indicators in mountain forest regions requires collection and evaluation of local data and their attributes. Genetic resources are listed among the core indicators for forest biological diversity. This study is a report on the evaluation of the standing genetic diversity within and across 12 pure beech stands (Fagus sylvatica L.) established within the CLIMO (CLImate Smart Forestry in MOuntain Regions) project, using nuclear microsatellite markers. The sampling sites were set along the species' distribution range, including the Balkan region and extending towards the Iberian Peninsula. Cores or leaves from 20 to 23 old, mature trees per plot were sampled for DNA analysis. Genetic diversity indices were high across the range (H-E = 0.74-0.81) with the highest in the Bosnian Mountains. Genetic divergence increased significantly with the geographical distance (Mantel test: r = 0.81, p < 0.001). Most of the stands exhibited an excess of heterozygotes, with the highest value at the Hungarian site (H-O/H-E = 1.177), where beech persists close to the eastern xeric limit of the species' distribution. STRUCTURE revealed within-region differentiation in the Balkan Peninsula, where the Bulgarian stand was the most outstanding. The genetic parameters of each stand could be assessed as a resource for CSF indicators interpreted especially at the local level.The authors acknowledge the networking support by the COST (European Cooperation in Science and Technology) Action CLIMO (Climate-Smart Forestry in Mountain Regions -CA15226) financially supported by the EU Framework Programme for Research and Innovation HORIZON 2020. Michal Bosela was additionally supported by the Slovak Research and Development Agency (project Nos. APVV-15-0265 and APVV-19-0183)

Ultrasound Measurement of the Volume of Musculus Quadriceps after Knee Joint Injury

The monitoring of the recovery of femoral muscles, after the knee-joint injury, is possible by the method of ultrasound measurement of the muscular volume. In a clearly defined longitudinal study, our object was to standardize the method of ultrasound measurement of muscular volume and to evaluate its adequacy in practical application in quadriceps muscle rehabilitation. The ultrasound measurements of m. rectus femoris and m. vastus intermedius were conducted in three intervals: in the first 24 hours after the injury; after 1 week, when immobilization was removed; and after 6 weeks, when rehabilitation was finished. The study comprised 30 patients with knee-joint injury, and 30 asymptomatic subjects, who formed the control group. The results showed significant decrease of muscular volume (mm3) after joint immobilization on injured leg and a significant increase of volume after rehabilitation. The same differences were observed on healthy legs, but without significance. Within the same intervals, there were no changes in the muscular mass in the control group. M. rectus femoris was completely recovered in greater number of patients (54.1%), comparing to m. vastus intermedius (25.4%). We conclude that the ultrasound is an appropriate method for monitoring the process of muscular atrophy during immobilization, as well as the course of muscular restitution during the physical therap

Giant Pseudocyst of the Rectus Femoris Muscle – Repetitive Strain Injury in Recreational Soccer Player

We report a case of a traumatic pseudocyst, in a recreational soccer player, after rupture of rectus femoris muscle. 37-year-old male, with history of repetitive painful accidents, was examined because of a double fist-sized mass in the anterior thigh. Ultrasound examination revealed a cystic mass in the rectus femoris muscle. Surgical removal of the mass and proximal remnant of muscle was done. Primary healing and functional recovery was achieved. Histological analysis revealed pseudocyst filled with degenerating clot and surrounded with thick fibrous capsule. The repetitive strain muscle injury, with prolonged period of healing, can occur like pseudocyst

Diastereoselective Aldol Reaction of 7-Bromo-5-pyrido-1,4-benzodiazepin-2-one; Relative and Absolute Configuration of All Stereoisomers

Aldol reaction of C(3) carbanion of 7-bromo-5-pyrido-1,4-benzodia-zepin-2-one (1) with representative aliphatic and aromatic aldehydes and ketones afforded racemic mixtures syn/anti-7-bromo-3-(1\u27-hydroxy-1\u27-phenylmethyl)-1-methyl-5-(2\u27-pyridyl)-2,3-dihydro-1H-1,4-benzodiazepin-2-one (2/3), syn/anti-7-bromo-3-(1\u27-hydroxy-1\u27-phenylethyl)-1-methyl-5-(2\u27-pyridyl)-2,3-dihydro-1H-1,4-benzodiazepin -2-one (4/5) and syn/anti-7-bromo-3-(1\u27-hydroxy-2\u27-methylpropyl)-1-methyl-5-(2\u27-pyridyl)-2,3-dihydro-1H-1,4-benzodiazepin-2-one (6/7) with 60-85% diastereoselectivity. For prevailing diastereomeric racemates (±)-2 and (±)-4, syn relative configuration is deduced, whereas the prevailing diastereomer (±)-7 has anti configuration. Configurational assignment is based on NMR data and X-ray structure analysis, and the origin of inversion of diastereoselectivity is discussed. Racemic mixtures were separated on chiral HPLC column, and on the basis of the CD spectra (3R) absolute configuration was determined for (+)-enantiomers, and (SS) configuration for (-)-enantiomers. Consequently, (3R,1\u27S) configuration is assigned to syn-(+)-enantiomers and (3R,1\u27R)-configuration to anti-(+)-enantiomers. In an attempt to use enantiomerically pure compounds 2-7 as catalysts in asymmetric alkylation of benzaldehyde by diethylzinc, these ligands proved chemically and configuration-ally unstable