RESUMEN
Arylglycines are important pharmacophores present in several top-selling drugs. This compound class has now been made accessible from abundant aryl chlorides by a Pd-catalyzed Schöllkopf-type amino acid synthesis. In the presence of the catalyst methylnaphthyl(XPhos)-palladium bromide, the base lithium 2,2,6,6-tetramethylpyrrolidide and the additive ZnCl2 , tert-leucine-derived bis-lactim ethers were efficiently arylated at room temperature, reaching yields of 95 % and diastereoselectivities of 98 : 2. Hydrolysis gave the corresponding arylglycines in high enantiomeric excess.
RESUMEN
Redox-active N-(fluoromethoxy)benzotriazoles were made accessible from fluoroacetic acid and hydroxybenzotriazoles via electrodecarboxylative coupling. After alkylation, they become effective monofluoromethoxylation reagents, enabling the photocatalytic C-H functionalization of arenes. Thus, irradiation of 1-(OCH2 F)-3-Me-6-(CF3 )benzotriazolium triflate with blue LED light in the presence of [Ru(bpy)3 (PF6 )2 ] promotes the synthesis of diversely functionalized aryl monofluoromethyl ethers. This method allows the late-stage functionalization of biologically relevant structures without relying on ecologically problematic halofluorocarbons.
RESUMEN
Trihalide salts were found to efficiently promote photochemical dediazotizing halogenations of diazonium salts. In contrast to classical Sandmeyer reactions, no metal catalysts are required to achieve high yields and outstanding selectivities for halogenation over competing hydridodediazotization. Convenient protocols are disclosed for synthetically meaningful brominations, iodinations, and chlorinations of diversely functionalized derivatives.
RESUMEN
Halogen-bridged methylnaphthyl (MeNAP) palladium dimers are presented as multipurpose Pd-precursors, ideally suited for catalytic method development and preparative organic synthesis. By simply mixing with phosphine or carbene ligands, they are in situ converted into well-defined monoligated complexes. Their catalytic performance was benchmarked against state-of-the-art systems in challenging Buchwald-Hartwig, Heck, Suzuki and Negishi couplings, and ketone arylations. Their use enabled record-setting activities, beyond those achievable by optimization of the ligand alone. The MeNAP catalysts permit syntheses of tetra-ortho-substituted arenes and bulky anilines in near-quantitative yields at room temperature, allow mono-arylations of small ketones, and enable so far elusive cross-couplings of secondary alkyl boronic acids with aryl chlorides.
RESUMEN
In a combined experimental and computational study, the isomerization activity of the dinuclear palladium(I) complex [PdI (µ-Br)(Pt Bu3 )]2 towards allyl arenes, esters, amides, ethers, and alcohols has been investigated. The calculated energy profiles for catalyst activation for two alternative dinuclear and mononuclear catalytic cycles, and for catalyst deactivation are in good agreement with the experimental results. Comparison of experimentally observed E/Z ratios at incomplete conversion with calculated kinetic selectivities revealed that a substantial amount of product must form via the dinuclear pathway, in which the isomerization is promoted cooperatively by two palladium centers. The dissociation barrier towards mononuclear Pd species is relatively high, and once the catalyst enters the energetically more favorable mononuclear pathway, only a low barrier has to be overcome towards irreversible deactivation.
RESUMEN
A facile insertion of ruthenium into aromatic C-H and allylic C-N bonds are the key steps in a [Ru( p-cymene)Cl2]2-catalyzed ortho-C-H allylation of benzoic acids. This protocol allows drawing on the large pool of allylic amines for state-of-the-art ortho-functionalizations of arenes, turning neutral amines into leaving groups. Concise syntheses of biologically active compounds provide further evidence of the synthetic potential of this methodology.