RESUMO
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.
RESUMO
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.
RESUMO
5-Aryl-substituted pyrazol-3-ylphosphonates have been conveniently synthesized by 1,3-dipolar cycloaddition of 1-formamidovinylphosphonates and aryldiazomethanes under K2CO3/MeOH conditions at room temperature. These pyrazoles are formed in one pot via spontaneous elimination of formamide. Basic conditions prevent competitive formation of cyclopropylphosphonates. 3-Aryl substituted pyrazol-5-carboxylates can be synthesized by the same methodology from 1-arylvinylphosphonates and ethyl diazoacetate, although a stronger base NaH is necessary to ensure the success of the aromatization stage with the elimination of the diethoxylphosphoryl moiety.