7-β- and 10-β-Hydroxylated congeners of CAF-603; elucidation of absolute configuration of CAF-603 family,and their SAR studies in the anti-fungal activity

Novel 7-β- and 10-β-hydroxylated congeners of CAF-603 (4 and 5, respectively) were isolated from Trichoderma crassum. Relative configuration of 4 was determined by NOE experiments. Stereochemistry of 7-β-hydroxy group in 5 was established by a combination of vicinal ³J_H–H analyses and quantum chemical calculations. Absolute configurations of 4 and 5 were established by observing the Cotton effects of their bis(2-naphthoate) esters. T. crassum also produce known CAF-603 (1), 14-hydroxy and 8,9-β-epoxy derivatives (2 and 3, respectively). Present study first established the absolute configuration of CAF-603 family by taking their biosyntheses into account. Preliminary biological experiments revealed that the molecular target strictly recognizes the β-side of the cycloheptane ring.     

Kinetics of the Initial Stage of Gelation in Chitosan Solutions Containing Glutaric Aldehyde: Viscometric Study

The effects of glutaric aldehyde concentration C _GA(in the range from 0.07 to 0.2 wt %) and temperature T(from 20 to 65°C) on the kinetics of an increase in the effective viscosity _effof aqueous solutions of chitosans (C _CH= 2.4 wt %, pH 3.6, and ionic strength I= 0.05) with molecular masses equal to 33 × 10⁴and 55 × 10⁴and the degrees of substitution at N-acetyl and amino groups of 0.08 and 0.90, respectively were studied. The kinetic curves _eff(t) exhibited the induction periods of a relatively slight increase in the viscosity of chitosan–glutaric aldehyde mixed solutions with time followed by the periods of a drastic increase in the viscosity. The former periods correspond to the formation of gel clusters; the latter periods, to the gelation over the whole volume of a solution. Optimal ranges of the parameters C _GAand Twere determined for the preparation of spherical gel particles of slightly cross-linked chitosan, which are used for the sorption of heavy metals from low-concentrated solutions.     

Synthesis and spatial structure of new chiral dopants from allobetuline series for cholesteric liquid-crystal compositions

Structural Chemistry - New series of chiral dopants for cholesteric liquid-crystal compositions were synthesized on the base of 2-substituted allobetuline derivatives, and their steric structure...     

A note on infinite aS-groups

Let G be a group. If every nontrivial subgroup of G has a proper supplement, then G is called an aS-group. We study some properties of aS-groups. For instance, it is shown that a nilpotent group G is an aS-group if and only if G is a subdirect product of cyclic groups of prime orders. We prove that if G is an aS-group which satisfies the descending chain condition on subgroups, then G is finite. Among other results, we characterize all abelian groups for which every nontrivial quotient group is an aS-group. Finally, it is shown that if G is an aS-group and |G| ≠ pq, p, where p and q are primes, then G has a triple factorization.     

A minimalist NMR approach for the structural revision of mucoxin

In an attempt to revise the structural assignment of mucoxin, and faced with 64 diastereomeric possibilities, we resorted to the synthesis of truncated structures that contained the core stereochemical sites. Twelve stereochemical analogues were synthesized, their (1)H and (13)C NMR spectra were analyzed and four recurring stereochemical trends were distilled from the data. Applying the observed trends to the diastereomeric population pared the possible choices for the correct structure of mucoxin from 64 to 4. Synthesis of these analogues led to the identification of the correct structure of mucoxin.     

New N-heterocyclic carbene palladium complex/ionic liquid matrix immobilized on silica: application as recoverable catalyst for the Heck reaction

[reaction: see text] A new concept of simultaneous covalent anchoring of a N-heterocyclic carbene palladium/ionic liquid matrix on the silica surface and the application of the resulting catalyst in the Heck reaction of a variety of different haloarenes is described. The catalyst shows high thermal stability (up to 280 degrees C) and could be recovered and reused for four reaction cycles, giving a total TON congruent with 36 600. Furthermore, TEM coupled with EDX analysis indicate the formation of Pd nanoparticles within the immobilized IL layer.     

β-Cyclodextrin as an efficient catalyst for the one-pot synthesis of 1-aminophosphonic esters in water

A simple, efficient, and general method has been developed for the one-pot synthesis of α-aminophosphonic esters in water using β-cyclodextrin as an efficient catalyst. α-Aminophosphonic esters were obtained in good yields (45-82%) and purity under mild conditions by the reaction of diethyl phosphite with a mixture of aldehyde and amine in water at reflux.     

Selective oxidation of sulfides to sulfoxides using 30% hydrogen peroxide catalyzed with a recoverable silica-based tungstate interphase catalyst

Various types of aromatic and aliphatic sulfides are selectively oxidized to sulfoxides and sulfones in good to excellent yields using 30% H2O2 in the presence of catalytic amounts of a novel recoverable silica-based tungstate interphase catalyst at room temperature. The catalyst can be recovered and reused for at least eight reaction cycles under the described reaction conditions without considerable loss of reactivity. [reaction: see text]