Enantiogroup‐Differentiating Biocatalytic Reductions of Prochiral Cs‐Symmetrical Dicarbonyl Compounds to meso Compounds

The stereoselective reduction of symmetrical prochiral dicarbonyl compounds bearing enantiotopic carbonyl groups yields several stereogenic centers in one step. In a proof‐of‐concept study, a new approach is described for the enzymatic desymmetrization of 5‐nitrononane‐2,8‐dione via sequential biocatalytic reduction steps utilizing ketoreductases to yield all possible diastereomers of 5‐nitrononane‐2,8‐diol.     

Toward a Better Understanding on the Adsorption Behavior of Aromatics in 12R Window Zeolites

Benzene adsorption behavior in a large family of 12R window zeolites (X, Y, EMT, Beta and LTL) has been examined by means of in-situ FTIR spectroscopy and correlated with the zeolite structure, the type and number of counter-ions, and the negative charge on framework oxygen atoms of zeolites. The effect of coadsorption of HCl, NH₃ and CH₃NH₂ on the benzene location has also been studied. The present work illustrates that besides the benzene adsorption on counter ions of zeolites, the 12R windows could also be the adsorption sites for benzene. Upon adsorption of coadsorbates such as HCl, NH₃ and CH₃NH₂, the migration of preadsorbed benzene molecules from one type of adsorption sites towards another, i.e. from 12R windows towards the cations for HCl and opposite direction for NH₃ and CH₃NH₂, has been evidenced. The lack of adsorption of benzene on 12R windows of NaBeta even upon coadsorption of a series of basic molecules reveals that benzene adsorption on 12R windows is most likely governed by a molecular recognition effect where benzene molecule and 12R window should have the adapted chemical and structural properties like in enzyme-substrate system and zeolites can be referred to as solid enzymes or zeo-enzymes. This paper indicates also that the adsorption properties of zeolites can be modified and accommodated by introduction of a co-adsorbate.     

Metalation and halogen‐metal exchange in the imidazo[1,2‐a]quinoxaline series

The n‐butyllithium and lithium 2,2,6,6‐tetramethylpiperidide metalation and the halogen‐metal exchange of imidazo[1,2‐a]quinoxaline derivatives followed by quenching with various electrophiles were studied. The reaction conditions have been optimized and various C₁ substituted imidazo[1,2‐a]quinoxalines were obtained in high yields.     

Nitrone in l-lyxose series: cycloaddition way for the synthesis of new C-α-fucosides

Nitrone 3 analogue of 5-deoxy-l-lyxose was derived from d-ribose. Its reduction with aqueous SO₂ gave the corresponding 4-amino-sugar 2, a potent α-l-fucosidase inhibitor. 1,3-Dipolar cycloaddition of 3 with alkenes allowed the synthesis of acetohydroxamic acid and ethane-phosphonate derivatives. Hydroxy-ethane derivative 15 is a nanomolar α-l-fucosidase inhibitor.