Green procedure for one-pot synthesis of azelaic acid derivatives using metal catalysis

Background & Objective: A green one-pot synthesis of oleic acid (1) derivatives is promoted by Rare Earth Metal (REM) triflates and commercial Molybdenum dioxo dichloride (MoCl 2 O 2 ) in the presence hydrogen peroxide as a green oxidant. Results: The protocol permits to govern the oxidation selectivity by simply choosing the proper combination of Mo and Sc catalysts. Conclusion: Methyl oleate epoxide 2a and azelaic acid 6 thus obtained are valuable industrial intermediates for synthesizing bio-compostable plastics, plasticizers of PVC, lubricating oils, cosmetics and pharmaceuticals (bactericides, anti-inflammatories, etc.)

Copper-mediated Regio- and Enantio-selective Cross-coupling of Heterocyclic Allyl Sulphides with Organomagnesium Compounds: A Case of 1,7-Relative Stereogenesis

Optically active heterocyclic allyl sulphides 1.7 react with organomagnesium compounds in the presence of CuBr to afford optically active alkenes in good yields and very high T-selectivity. The regioselectivity depends on the solvent as well on the CuBr: allylic sulphide ratio. The heterocyclic nucleus imparts asymmetric induction in the range of 50-98% ee. The regio- and enantio-selectivity of these reactions would be related to the coordination exerted by the heterocyclic nitrogen toward the copper organyi

Allylated Ketosulphides of Benzothiazole as Intermediates for Stereoselective Synthesis of Allyl Ketones, Allyl Thiiranes and Dienes

alfa-Ketosulphides of benzothiazole 1 react with allylic carbonates in the presence of palladium acetate in dichloromethane under mild conditions affording alfa- and alfa,alfa-diallylated ketosulphides 2 in high yields. Reductive desulphurization of 2a-d with tributyltin hydride gives diallylated ketones 3s-d, whereas reduction of mono-allylated Ze-k with sodium borohydride in isopropanol affords ally1 episulphides 4e-k prevalently as (Z)-isomers which can be transformed stcteoselectively into dienes