New trends in the chemistry of α-fluorinated ethers, thioethers, amines and phosphines

Fluorine, the most electronegative element plays nowadays a key role in pharmaceutical, agrochemical and material sciences. About 20% of all pharmaceuticals and about 30% of agrochemicals under development or recently introduced on the market contain fluorine. However, when one examines the relevant structures more closely, one quickly recognizes a structural monotony. The same fluorine bearing aromatic or heterocyclic “cores” appear over and over again. The search for novel molecules having “emergent” fluorinated groups and the development of an efficient access toward them is a challenging task for industrial as well as academic laboratories. For example, the trifluoromethoxy group finds increased utility as a substituent in bioactives, but it is still perhaps the least well understood fluorine substituent in currency. The present review will give an updated overview on the synthesis of α-fluorinated ethers, thioethers, amines and phosphines.     

A Simple Synthesis of the Natural 2,5-Dialkylresorcinol Free Radical Scavenger Antioxidant: Resorstatin

3,5-Dimethoxybenzoic acid 3 has been transformed into olivetol dimethyl ether 6 in three steps in 79% yield. Directed ortho-metallation-alkylation of 6, followed by boron tribromide demethylation resulted in a simple and inexpensive synthesis of resorstatin, in 70% overall yield from 3.     

A Convenient Synthesis of Triarylbismuth Diacetates

Triarylbismuthanes react with sodium perborate in acetic acid under mild conditions to afford triarylbismuth diacetates in good yields. This method is fast, efficient and environmentally friendly.     

Synthesis of Furoates and Furfurylic Alcohol Esters Under Very Mild Conditions Using Supported Base Catalysis

Sym-phthaloyl chloride under controlled cathodic reduction is converted into trans-[1(3H)-isobenzofuranone, 3-(3-oxo-1(3H)-isobenzofuranylidene)]: trans-biphthalyl in 65% yield.     

Synthesis of C-Ring Hydroxylated Neoflavonoids by Ligand Coupling Reactions

Reaction of 4-trifluoromethanesulfonyloxycoumarin derivatives with benzyloxyphenylboronic acid derivatives under modified Suzuki reaction conditions afforded the corresponding neoflavones. Selective debenzylation took place in high yields when the palladium-catalysed hydrogenolysis was performed in the presence of acetic acid.     

Corrections to the scaling of the second-order structure function in isotropic turbulence

The approach of Obukhov assuming a constant skewness was used to obtain analytical corrections to the scaling of the second order structure function, starting from Kolmogorov＇s 4/5 law. These corrections can be used in model applications in which explicit expressions, rather than numerical solutions are needed. The comparison with an interpolation formula proposed by Batchelor, showed that the latter gives surprisingly precise results. The modification of the same method to obtain analytical corrections to the scaling law, taking into account the possible corrections induced by intermittency, is also proposed.     

Binary clustering

In many clustering systems (hierarchies, pyramids and more generally weak hierarchies) clusters are generated by two elements only.This paper is devoted to such clustering systems (called binary clustering systems). It provides some basic properties, links with (closed) weak hierarchies and some qualitative versions of bijection theorems that occur in Numerical Taxonomy. Moreover, a way to associate a binary clustering system to every clustering system is discussed.Finally, introducing the notion of weak ultrametrics, a bijection between indexed weak hierarchies and weak ultrametrics is obtained (the standard theorem involves closed weak hierarchies and quasi-ultrametrics).     

A new method of bromination of aromatic rings by an iso-amyl nitrite/HBr system

A mixture of iso-amyl nitrite/HBr is shown to be a mild and efficient reagent for electrophilic aromatic bromination. The reaction succeeds with slightly activated arenes and heterocyclic compounds. By using HCl instead of HBr, chlorination can also be performed in few cases. The i-amONO₂/HBr mixture can also be utilized for bromination in the α-position of electron withdrawing groups. A possible mechanism is briefly discussed.