The diastereoselective synthesis of unsaturated aromatic 1,2-amino alcohols can be achieved on an epimeric mixture of optically active allylic ethers having a hydroxyl group attached to an allylic chiral center to the pi-system using chlorosulfonyl isocyanate. These reactions produced the unsaturated anti-1,2-amino alcohols either exclusively or predominantly only for aromatic derivatives. The ...

Gold(i)-catalysed addition of alcohols to 3,3-disubstituted cyclopropenes occurs in a highly regioselective and facile manner to produce alkyl tert-allylic ethers in good yields. The reaction is tolerant of sterically hindered substituents on the cyclopropene as well as primary and secondary alcohols as nucleophiles. In this full article, we report on the substrate scope and plausible mechanism...

The enantioselective silylation of racemic alcohols, where one enantiomer reacts faster than the other, is an alternative approach to established enzymatic and non-enzymatic acylation techniques. The existing art is either limited to structurally biased alcohols or requires elaborate catalysts. Simple substrates, such as benzylic and allylic alcohols, with no coordinating functionality in the p...

An efficient and one-pot procedure for the synthesis of arylated and stereodefined allylic alcohols has been achieved through zirconium-mediated multicomponent coupling reactions of alkynes, aldehydes (or ketones), and aryl iodides. The subsequent intramolecular Friedel-Crafts reactions of these allylic alcohols catalyzed by Brønsted or Lewis acids afford highly substituted indenes and spiroind...

Friedel-Crafts allylic alkylation of a wide variety of aromatic and heteroaromatic compounds with allylic alcohols catalysed by AuCl(3) (5 mol%) under mild conditions at room temperature was accomplished in good to excellent yields (up to 99%) and regioselectivity.

Palladium catalyzed allylic C-H functionalization was performed using exocyclic alkene substrates. Multi-component synthesis of stereodefined homoallylic alcohols could be performed using a reaction sequence involving allylic C-H borylation and allylation of aldehydes.

The rhodium-catalyzed oxidative amidation of allylic alcohols and aldehydes is reported. In situ generated [(BINAP)Rh]BF4 catalyzes the one-pot isomerization/oxidative amidation of allylic alcohols or direct amidation of aldehydes using acetone or styrene as the hydrogen acceptor. The conditions are general, affording good to excellent yields with a wide array of amine and aniline nucleophiles,...

Stereospecific [3,3]-sigmatropic rearrangement of O-substituted thiocarbamate derivatives of enantiopure allylic alcohols provides allylic thiocarbamates as single enantiomers. Intramolecular arylation by rearrangement of their allyllithium derivatives provides allylic tertiary thiols. Allylation and ring-closing metathesis gives 2,5-dihydrothiophenes containing sulfur-bearing quaternary centres.

Rhenium-catalyzed stereoselective transposition of allylic alcohols is reported.

[reaction: see text] A useful method for the conversion of prochiral allylic alcohols to chiral allylic amines of high enantiopurity is reported. N-(4-Methoxyphenyl)trifluoroacetimidates are excellent substrates for the palladium(II)-catalyzed allylic imidate rearrangement as the allylic trifluoroacetamide products can be deprotected in two steps to provide chiral nonracemic allylic amines. Di-...