Described herein is a Pd-catalyzed haloallylation of aromatic ynol ethers and allyl chlorides, allowing facile access to (1E)-α-chloroenol ethers in a highly regio- and stereoselective manner. The synthetic utility of this method is demonstrated well by the synthesis of the stereodefined multisubstituted enol ethers and α-allylated carbonyl compounds.

Highly diastereoselective and enantioselective catalytic capture of chiral zinc enolates using nitroolefins as electrophiles is described. The tandem products γ-nitro ketones were obtained in good yields with high diastereoselectivities and enantioselectivities. The γ-nitro ketones were readily hydrogenated to the optically enriched and diastereomerically pure chiral pyrrolidines with four cont...

Although phase-transfer-catalyzed asymmetric S(N)Ar reactions provide unique contribution to the catalytic asymmetric α-arylations of carbonyl compounds to produce biologically active α-aryl carbonyl compounds, the electrophiles were limited to arenes bearing strong electron-withdrawing groups, such as a nitro group. To overcome this limitation, we examined the asymmetric S(N)Ar reactions of α-...

The design and development of an extraordinarily interesting new class of chiral sulfur-olefin hybrid ligands with remarkable structural simplicity were described. These unique sulfinamide-olefin ligands have been proved to be highly effective ligands in rhodium-catalyzed asymmetric 1,4-addition reactions of aryl boronic acids to α,β-unsaturated carbonyl compounds (up to 99% yield and 98% ee).

The palladium-catalysed intramolecular α-arylation of carbonyl compounds with amino-tethered 2- and 3-iodoindoles provides a useful methodology for the synthesis of indolo-b-fused nitrogen heterocycles. A variety of substituted tetrahydro β- and γ-carbolines, and pyrrolo[3,4-b]indoles, have been prepared by means of this palladium-catalysed annulation process.

Bis(2,4,6-triisopropylphenyl) tellurone (Tip(2)TeO(2)) was prepared, fully characterized by spectroscopic and X-ray crystallographic analyses, as well as theoretical calculations, and found to be an effective oxidizing agent that was capable of converting alcohols into carbonyl compounds under mild reaction conditions.

A remarkable α-effect of silicon has been discovered that results in soft nucleophilicity at the Cγ of 3,3-bis(silyl) allyloxy lithium 1. The addition of 1 to α,β-unsaturated carbonyl compounds, including enals, proceeds in a 1,4- over 1,2-manner with medium to good regioselectivity, whereas the parent allyloxy lithium 4 undergoes complete 1,2-addition. The results from DFT calculations of HMPA...

An efficient and operationally simple synthesis of fluoroalkanes by deoxygenative hydrofluorination of carbonyl compounds via their tosylhydrazone surrogates is reported. The reaction can be carried out in a one-pot procedure directly from carbonyl compounds.

Recent advances in the palladium-catalyzed remote functionalization of carbonyl derivatives are highlighted in this review. The structure of the article is based on the three strategies that have emerged in recent years as the most viable tactics to construct C(sp(3))-C, C(sp(3))-N or C(sp(3))-O bonds at a distance of at least three carbon atoms from the carbonyl functionality. The specific asp...

The preparation of alkynes from carbonyl compounds via a one-carbon homologation has become a very useful pathway for the synthesis of acetylenic compounds, both internal and terminal. This tutorial review provides an overview of the different methods available for this transformation, including their scope and limitations, recent developments and applications in total syntheses.