Asymmetric transition-metal-catalyzed allylic alkylations: applications in total synthesis.

Ferrocenyl bis-phosphine ligands bearing sulfinyl, sulfonyl or sulfenyl groups: applications in asymmetric hydrogenation and allylic alkylation reactions

A new series of chiral ferrocenyl bis-phosphine ligands have been synthesized. Elements of planar and central chirality have been incorporated into a ferrocene backbone through sulfinyl, sulfonyl and sulfenyl groups at the ortho-position to the phosphines. The effectiveness of these ligands has been demonstrated in Rh-catalyzed hydrogenations and Pd-catalyzed allylic alkylations. 2005 Elsevier ...

Gold(I)-catalyzed enantioselective synthesis of benzopyrans via rearrangement of allylic oxonium intermediates.

The first transition metal catalyzed asymmetric carboalkoxylation reaction of propargyl esters is described. The (R)-MeO-DTBM-BIPHEP(AuCl)(2)-catalyzed reactions allow for the construction of benzopyrans containing quaternary stereocenters with excellent enantioselectivity. Experimental evidence supports a mechanism proceeding via the generation of a stabilized carbocation from an allylic oxoni...

Enantioselective transition metal-catalyzed allylic

tions have been developed as fundamentally important crosscoupling reactions. In general, the heteroatom nucleophiles in these reactions have been largely limited to alkylamines, anilines, carboxylates and phenols. Our laboratory is interested in searching the synthetically useful heteroatom nucleophiles for the synthesis of functionalized allylic compounds (Fig. 1). As our successful examples,...

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.

Pd-catalyzed asymmetric allylic alkylations via C–H activation of N-allyl imines with glycinates† †Electronic supplementary information (ESI) available: Additional details of experimental methods and results. See DOI: 10.1039/c7sc02899g Click here for additional data file.