Solid-state photodimerization of steroid enones

Androst-4-ene-3,17-dione (1) and 17alpha-methyltestosterone (2) are dimerized in the solid-state by UV radiation. These substances were selected by a search in the CSD among the steroid enones presenting in the crystalline state an intermolecular short contact between a hydrogen alpha to a carbonyl group and the oxygen of an enone system. Dimerization occurs by transfer of the hydrogen to the oxygen and connection between the two involved carbons. Androst-4-ene-3,17-dione (1) affords dimer 3 and trimer 4, both formed by connection of the C-16 of a molecule with the C-3 of a near one. Irradiation of 17alpha-methyltestosterone (2) gives the isomeric trienones 5 and 6. These compounds are reasonably formed by dehydration of unisolated intermediate products 7 and/or 8 obtained by coupling of two molecules through a linkage between the C-2 and the C-3' carbons. The formation mechanisms of the photoproducts are satisfactory explained on the basis of the molecular arrangement of the monomers in the crystal state. Modeling of the dimeric molecules was done using molecular mechanics calculations. A single-crystal X-ray of the dimer of androst-4-ene-3,17-dione confirms the structural interpretation of spectral data. The conformer found in the solid-state agrees well with the results of molecular mechanics calculations.     

Solvent-free Mukaiyama aldol reaction of O-silyl dienolates catalyzed by benzoic acid

The vinylogous aldol reaction of O-silyl dienolates deriving from 2,2-dimethyl-[1,3]-dioxin-4-ones proceeds in moderate to excellent yields in the presence of catalytic amounts of PhCOOH under solvent-free conditions. Modest to good yields can be obtained by using silica gel or 3 Å molecular sieves as heterogeneous catalysts.     

A new synthesis of 4-methoxy-cyclopent-2-en-1-ones

4-methoxy-cyclopent-2-en-1-ones $\text{6}$ are easily obtained through a simple procedure involving in the key-step the conversion of 2-furylcarbinols $\text{1}$ into 1,1,2-trimethoxy-al-kan-4-ones $\text{3}$, a masked form of 1,4-dicarbonyl compounds, by treatment with Amberlyst H15 in methanolic solution. Then, the regeneration of the aldehydic function and a base-catalysed aldolic condensation lead in high yields to the final products $\text{6}$.     

Convenient procedure of Horner-Wadsworth-Emmons olefination for the synthesis of simple and functionalized α,β-unsaturated nitriles

A mild and practical procedure of Horner-Wadsworth-Emmons olefination promoted by lithium hydroxide and α-cyano phosphonates has been set up for the synthesis of α,β-unsaturated nitriles. The reaction conditions are tolerated by functionalized ketones and the exclusive formation of E-γ-hydroxy α,β-unsaturated nitriles has been observed.     

Enhancing selectivity in oxidation catalysis with sol-gel nanocomposites

Valuable organic compounds such as alpha-hydroxy acids are easily synthesised with relevant selectivity enhancement using a sol-gel hydrophobized nanostructured silica matrix doped with the organocatalyst TEMPO: A materials science based synthetic route which cannot be achieved via classical homogeneous synthesis.     

Right distributive quasigroups on algebraic varieties

In this paper we develop a structure theory of algebraic right distributive quasigroups which correspond to closed and connected conjugacy classes generating algebraic Fischer groups (in the sense of [6]) such that the mappingx x ^–1 ax, fora , is an automorphism of (as variety). We also give examples of algebraic Fischer groups where this does not happen. It becomes clear that the class of algebraic right distributive quasigroups has nice properties concerning subquasigroups, normal subquasigroups and direct product.We give a complete classification of one- and two-dimensional as well as of minimal algebraic right distributive quasigroups.     

Reactions of ketenes. XX. Phenylketene dimethylacetal as synthon for the introduction of functionalized phenylethyl units

Phenylketene dimethylacetal ( 1 ) reacts with the α-diazoketones to give the dihydrofurans 6 . These compounds, as cyclic ortho esters, can undergo dealcoholation into the furans 2 and hydrolysis into the γ-ketoesters 3 and into the γ-ketoacids 4 . Cyclopropane acetal 8 , obtained starting from acetal 1 and ethyl diazoacetate, by heating leads quantitatively to functionalized ester 9 . These synthetic methods enlarge the sphere of applicability of the electron-rich alkene 1 as synthon in organic synthesis.     

Stereospecific uncatalyzed alpha-O-glycosylation and alpha-C-glycosidation by means of a new D-Gulal-derived alpha vinyl oxirane

The reaction of alpha vinyl oxirane 5, prepared through a new route to the d-gulal system, with O-nucleophiles (alcohols and di-O-isopropylidene-alpha-d-monosaccharides) and C-nucleophiles (lithium alkyls) affords, in a completely stereoselective way, the corresponding 2-unsaturated alpha O- and C-glycosides having the same configuration as the starting epoxide.     

Heterocyclic steroids—III : The synthetic utility of a 2-furyl steroid

Preparation and reactions of the 2-furyl steroid 4 is described. In acidic medium, a product, 8, arising from furan ring opening with the introduction of functional groups in 23,25 and 26 carbon atoms, is observed. In slightly different experimental conditions, 4 yields a product 10 of a new molecular rearrangement, involving the 3 oxocyclopentene-5 hydroxy unit in the steroid side chain.