Stereoselective Syntheses of 2-Methyl-1,3-diol Acetals via Re-Catalyzed [1,3]-Allylic Alcohol Transposition

Regio- and stereocontrol in rhenium-catalyzed transposition of allylic alcohols.

A hydroxyl group-directed, highly regio- and stereoselective transposition of allylic alcohols based on rhenium catalysis has been developed. The method is suitable for a direct isomerization of acetals into the thermodynamically preferred isomer as long as one of the hydroxyl groups is allylic. This method will expand the scope of rhenium-catalyzed alcohol transpositions for complex molecule s...

Stereoselective palladium-catalyzed allylic alkylations of peptide amide enolates.

Pd-catalyzed allylations are an excellent tool for stereoselective peptide modifications, being clearly superior to normal alkylations. The reactions proceed not only in high yield, but also high regio- and diastereoselectivities, and trans-products are formed exclusively. Therefore, this is a powerful synthetic tool for natural product and drug synthesis.

Iridium-Catalyzed Stereoselective Allylic Alkylation Reactions with Crotyl Chloride.

The development of the first enantio-, diastereo-, and regioselective iridium-catalyzed allylic alkylation reaction of prochiral enolates to form an all-carbon quaternary stereogenic center with an aliphatic-substituted allylic electrophile is disclosed. The reaction proceeds with good to excellent selectivity with a range of substituted tetralone-derived nucleophiles furnishing products bearin...

Chemo- and regioselective reductive transposition of allylic alcohol derivatives via iridium or rhodium catalysis.

We report highly chemo- and regioselective reductive transpositions of methyl carbonates to furnish olefin products with complementary regioselectivity to that of established Pd-catalysis. These Rh- and Ir-catalysed transformations proceed under mild conditions and enable selective deoxygenation in the presence of functional groups that are susceptible to reduction by metal hydrides.

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