Organoaluminum compounds reaction with epoxides

Reaction with epoxy aiochols-3 Epoxides formed from (E)-allylic alcohols react regioselectively with organoaluminum compounds to provide 1,2-diols with inversion at C j in high yield. 

Aluminum tetraphenylporphyrin with axial bound chloride, (TPP)AICI, Ic is an effective initiator for the anionic ringopening polymerization of epoxides (11). - - This complex can be easily synthesized by reacting free-base tetraphenylporphyrin, (TPP)H2, with chlorodiethylaluminum in CH2CI2 under nitrogen, where the reaction proceeds rapidly and quantitatively at room temperature with evolution of two equivalents of ethane with respect to (TPP)H2-According to Scheme 1, a variety of aluminum porphyrins can be synthesized using some organoaluminum compounds and they are easily identified by H NMR (Table 2). 

The Reformatskii reaction can be carried out conveniently with magnesium. If tert-huiy esters are used, the products can subsequently be transformed into satd. acids in a single operation Another easy method for the conversion of aldehydes to nitriles is their treatment with lead tetraacetate and ammonia in benzene Hydrocyanations can be efficiently performed with the help of organoaluminum compounds In this manner, steroidal cyanohydrins can be obtained from the respective epoxides by diaxial fission under mild conditions in high yield A number of addition reactions of nitrile oxides have been reported contrary to earlier reports, ar. nitrile oxides easily add hydrogen halides. 

Abstract The use of organoaluminum-based Lewis acids (A1R X3 R = alkyl, alkynyl, X = halide or pseudohalide) in the period 2000 to mid-2011 is overviewed with a focus on (1) stoichiometric reactions in which one of the organoaluminum substituents is transferred to the substrate (e.g., the opening of epoxides, 1,2-additions to carbonyl compounds, coupling with C-X, and Reissert chemistry) and (2) asymmetric, often catalytic, reactions promoted by Lewis acid catalysts derived from organoaluminum species (e.g., use of auxiliaries with alanes, Diels-Alder, and related cycloaddition reactions, additions to aldehydes and ketones, and skeletal rearrangement reactions). 

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