Pd-catalyzed asymmetric allylic alkylations via C-H activation of N-allyl imines with glycinates.

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.

Kinetic resolution of primary allylic amines via palladium-catalyzed asymmetric allylic alkylation of malononitriles.

A range of primary allylic amines were resolved with selectivity factors of up to 491 through [Pd(allyl)Cl]2/(S)-BINAP-catalyzed and mesitylsulfonyl hydrazide-accelerated asymmetric allylic alkylation of malononitriles involving enantioselective C-N bond cleavage under aerobic conditions. Moreover, the reaction proved useful for the asymmetric synthesis of α-branched allyl-substituted malononit...

Ligand bite governs enantioselectivity: electronic and steric control in Pd-catalyzed allylic alkylations by modular fenchyl phosphinites (FENOPs).

Modular fenchyl phosphinites (FENOPs) containing different aryl units-phenyl (1), 2-anisyl (2), or 2-pyridyl (3)-are efficiently accessible from (-)-fenchone. For comparison of the influence of the different aryl units on enantioselectivities and reactivities, these FENOPs were employed in Pd-catalyzed allylic alkylations. The strongly chelating character of P,N-bidentate 3 is apparent from X-r...

Design of bifunctional chiral phenanthroline ligand with Lewis basic site for palladium-catalyzed asymmetric allylic substitution.

Conceptually new bifunctional chiral ligands were developed. The axially chiral N,N-bidentate phenanthroline ligand (S)-1 was found to be effective for Pd-catalyzed asymmetric allylic substitution of allyl acetate and dialkyl malonate. The intramolecular Lewis basic group from the hydroxybinaphthyl structure of (S)-1 played a pivotal role in the high reactivity and enantioselectivity.

Allylic sp3 C-H borylation of alkenes via allyl-Pd intermediates: an efficient route to allylboronates.

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.