TADDOL-based P,S-bidentate phosphoramidite ligands in palladium-catalyzed asymmetric allylic substitution.

A series of easy-to-prepare and modular chiral P,S-bidentate phosphoramidites were synthesized. With respect to Pd(II), these ligands showed the ability to form stable P,S-chelate allylic complexes. The structures of the ligands and their complexes were confirmed by 2D NMR spectroscopy and single-crystal X-ray diffraction. These chiral inducers provided up to 99% ee in the Pd-catalyzed asymmetric allylic substitution of (E)-1,3-diphenylallyl acetate with C- and N-nucleophiles and up to 94% ee in the Pd-mediated allylic alkylation of cinnamyl esters with ß-ketoesters and 2,5-dimethylpyrrole. Furthermore, up to 92% ee with quantitative conversion and chemo- and regioselectivity was achieved in the rare reaction between 2-(diethoxyphosphoryl)-1-phenylallyl acetate and aniline. The effects of the structural parameters, reaction conditions and ligand-to-metal ratio on the catalytic results are discussed. It was shown that the ligands surpass their analogues with different denticity.

Diamidophosphites from ß-hydroxyamides: readily assembled ligands for Pd-catalyzed asymmetric allylic substitution.

Two groups of modular chiral diamidophosphite ligands were easily synthesised from accessible N-Boc-amino alcohols and pseudodipeptides. The reaction of these compounds with [Pd(allyl)Cl]2 in the presence of AgBF4 yielded complexes [Pd(allyl)(L)2]BF4. In addition, metallochelates [Pd(allyl)(L)]BF4 with (S)-methioninol-based P,S-bidentate ligands were prepared. The structures of the novel ligands and complexes were elucidated by means of 2D-NMR and were confirmed by single-crystal X-ray diffraction, as well as by DFT calculations. Asymmetric inducers of this type exhibited high enantioselectivities in the Pd-mediated allylic substitution of (E)-1,3-diphenylallyl ethyl carbonate with CH2(CO2Me)2 (up to 98% ee) and (CH2)4NH (up to 92% ee). Ee values of up to 86% and 73% were obtained in the Pd-catalyzed allylic alkylation of cinnamyl acetate with ethyl 2-oxocyclohexane-1-carboxylate and ethyl 2-oxocyclopentane-1-carboxylate, respectively. The effects of the structural modules, such as the nature of the phosphorus-containing ring or exocyclic substituent, on the catalytic activity and enantioselectivity were investigated.

(S)-6-Bromo-BINOL-based phosphoramidite ligand with C(1) symmetry for enantioselective hydrogenation and allylic substitution.

(S)-6-Br-BINOL-derived phosphoramidite, a simple monodentate ligand with a stereogenic center at the phosphorus atom, was synthesized for the first time. This stereoselector generated a high level of enantioselectivity (80-95% ee) in the rhodium-catalyzed hydrogenation of alpha-dehydrocarboxylic acid esters and was also successfully employed in the asymmetric palladium-catalyzed allylic substitution of (E)-1,3-diphenylallyl acetate. The optical yield also showed significant dependence with reaction type: up to 70% ee for allylic amination, up to 75% ee for allylic sulfonylation, and up to 90% ee for allylic alkylation.

Novel P,N-bidentate phosphite ligands in asymmetric catalysis.

Results achieved by the authors in the synthesis of chiral P,N-phosphite ligands are summarized. Three groups of new chiral P,N-phosphites are discussed, namely, ligands derived from 1,1'-bi-2-naphthol, ligands possessing an acyclic phosphorus center, and P*-chiral ligands derived from (S)-2-anilinomethylpyrrolidine. An overview of complexation of the ligands with Rh(I) and Pd(II) precursors is given. Accessibility and stability of chiral phosphite ligands possessing acyclic phosphorus was analyzed for the first time along with their efficiency in terms of stereoselectivity. The title ligands are shown to be highly efficient in the Pd-catalyzed allylic alkylation (up to 85% ee) and, especially, allylic sulfonylation (up to 97% ee) reactions in certain cases outperformed all known catalytic systems.