Massimo Massaccesi

LiClO4-acyl anhydrides complexes as powerful acylating reagents of aromatic compounds in solvent free conditions

Abstract The Friedel–Crafts acylation of various activated benzenes is smoothly carried out with acyl anhydrides in the presence of 2 equiv. of LiClO 4 , as reaction promoter, under solventless conditions.

One-pot highly stereoselective reduction of β-keto amides to syn-γ-aminols

Abstract In the presence of titanium tetrachloride, the borane/tetrahydrofuran complex can reduce 2-methyl-3-oxoamides into the corresponding syn -aminols in good yields and high diastereoselectivity. The use of borane/dimethyl sulfide instead of BH 3 /THF allows a partial reduction to syn -β-hydroxyamides.

Highly stereoselective titanium-mediated addition of organocerium reagents to β-keto amides: an efficient synthesis of stereodefined β-hydroxy amides having a tertiary alcoholic fragment

A highly efficient and stereoselective protocol for the TiCl4-mediated addition of organocerium reagents to β-keto amides is now available. The method allows the introduction of a large variety of carbon frameworks, including primary, secondary and tertiary alkyl chains, as well as aromatic, alkynylic and benzylic moieties, in high yields and with high stereoselection.

A Highly Diastereoselective TiCl4-Mediated Reduction of β-Hydroxy Ketones with BH3·py — A Very Efficient and General Synthesis of syn-1,3-Diols

β-Hydroxy ketones can be reduced to the corresponding 1,3-diols in high yields and with excellent diastereoselectivity by carrying out the reaction with BH3·pyridine in CH2Cl2 at −78 °C in the presence of TiCl4. This protocol is general and chemoselective: excellent results are obtained when the substituents are primary, secondary, tertiary alkyl chains or aromatic moieties. The presence of reducible functionalities such as bromide, nitro and cyano groups is well tolerated.