Intensification of Double Kinetic Resolution of Chiral Amines and Alcohols via Chemoselective Formation of a Carbonate–Enzyme Intermediate

Chiral amines and alcohols are synthons of numerous pharmaceutically-relevant compounds. The previously developed enzymatic kinetic resolution approaches utilize a chiral racemic molecule and achiral acyl donor (or acyl acceptor). Thus, only one enantiodivergent step of the catalytic cycle is engaged, which does not fully exploit the enzyme’s abilities. The first carbonate-mediated example of simultaneous double chemoselective kinetic resolution of chiral amines and alcohols is described. Herein, we established a biocatalytic approach towards four optically-pure compounds (>99% ee, Enantioselectivity: E > 200) via double enzymatic kinetic resolution, engaging chiral organic carbonates as acyl donors. High enantioselectivity was ensured by extraordinary chemoselectivity in lipase-catalyzed formation of unsymmetrical organic carbonates and engaged in a process applicable for the synthesis of enantiopure organic precursors of valuable compounds. This study focused not only on preparative synthesis, but additionally the catalytic mechanism was discussed and the clear impact of this rarely observed carbonate-derived acyl enzyme was shown. The presented protocol is characterized by atom efficiency, acyl donor sustainability, easy acyl group removal, mild reaction conditions, and biocatalyst recyclability, which significantly decreases the cost of the reported process.     

Chemical Characteristics of Ethanol and Water Extracts of Black Alder (Alnus glutinosa L.) Acorns and Their Antibacterial,Anti-Fungal and Antitumor Properties

The aim of this study was to identify polyphenolic compounds contained in ethanol and water extracts of black alder (Alnus glutinosa L.) acorns and evaluate their anti-cancer and antimicrobial effects. The significant anti-cancer potential on the human skin epidermoid carcinoma cell line A431 and the human epithelial cell line A549 derived from lung carcinoma tissue was observed. Aqueous and ethanolic extracts of alder acorns inhibited the growth of mainly Gram-positive microorganisms (Staphylococcus aureus, Bacillus subtilis, Streptococcus mutans) and yeast-like fungi (Candida albicans, Candida glabrata), as well as Gram-negative (Escherichia coli, Citrobacter freundii, Proteus mirabilis, Pseudomonas aeruginosa) strains. The identification of polyphenols was carried out using an ACQUITY UPLC-PDA-MS system. The extracts were composed of 29 compounds belonging to phenolic acids, flavonols, ellagitannins and ellagic acid derivatives. Ellagitannins were identified as the predominant phenolics in ethanol and aqueous extract (2171.90 and 1593.13 mg/100 g DM, respectively) The results may explain the use of A. glutinosa extracts in folk medicine.     

Triphenylamine derivatized phenylacetylene macrocycle with large two-photon absorption cross-section

A phenylacetylene macrocycle (PAM) derivative containing triphenylamine as the framework was synthesized in one-step Sonogashira coupling. The photophysical and electrochemical properties were investigated in details. This hexamer shows significant enhancement in two-photon absorption cross-section relative to reported PAM derivatives.     

Hydroindene-derived chiral synthons from carotol and their cytotoxicity

Ten enantiomerically pure hydroindene-derived compounds obtained by the transformation of (+)-carotol, the main constituent of carrot seed essential oil, were examined for their ability to inhibit the growth of myeloid leukaemia (HL-60) cancer cell lines. All compounds showed significant activity, which was comparable to the most active volatile organic compounds, such as trans–trans-farnesol, citral and nerolidol. Based on the bioactivity and molecular modelling, a 3D QSAR pharmacophore model was generated.     

Transformation of macromonomers into ring‐opening polymerization macroinitiators: A detailed initiation efficiency study

In the present study, n‐butyl acrylate macromonomer (BAMM) (M_n = 1900 g mol^?1; PDI = 1.96) has been synthesized via a high‐temperature polymerization process. Subsequently, the olefinic termini of the BAMM have been transformed into a diol via a dihydroxylation process using KMnO₄ as an oxidizing agent. The OH‐terminated macroinitiator pBA(OH)₂ has subsequently been employed for the ring‐opening polymerization (ROP) of ε‐caprolactone via various catalytic systems, that is, organo‐(1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene), metal (tin(II) 2‐ethylhexanoate), and enzymatic catalysis (Novozym® 435). The obtained pBA‐b‐pCL block copolymers and the initiation efficiency of the BAMM macroinitiator have been investigated via size exclusion chromatography (SEC), electrospray ionization–mass spectrometry (ESI‐MS) hyphenated with SEC and liquid chromatography at the critical conditions of both poly(ε‐caprolactone) (pCL) and pBA. The in vitro enzyme catalysis (eROP) approach proved to be the most efficient catalysis system due to minor transesterification side reactions during the polymerization process. However, side reactions such as transesterifications occur in each catalytic system and—while they cannot be suppressed—they can be minimized. The species generated during the eROP process include the desired block copolymer pBA‐b‐pCL as main species as well as pCL homopolymer and residual macroinitiator pBA(OH)₂. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012