Pd-catalyzed β-C–H functionalizations of carboxylic acid derivatives using an auxiliary as a directing group have been extensively explored in the past decade. In comparison to the most widely used auxiliaries in asymmetric synthesis, the simplicity and practicality of the auxiliaries developed for C–H activation remains to be improved. We previously developed a simple N-methoxyamide auxiliary to direct β-C–H activation, albeit this system was not compatible with carboxylic acids containing α-hydrogen atoms. Herein we report the development of a pyridine-type ligand that overcomes this limitation of the N-methoxyamide auxiliary, leading to a significant improvement of β-arylation of carboxylic acid derivatives, especially α-amino acids. The arylation using this practical auxiliary is applied to the gram-scale syntheses of unnatural amino acids, bioactive molecules and chiral bis(oxazoline) ligands.
An intermolecular C(sp(3))-H amination using a Pd(0) /PAr3 catalyst was developed. The reaction begins with oxidative addition of R2 N-OBz to a Pd(0) /PAr3 catalyst and subsequent cleavage of a C(sp(3))-H bond by the generated Pd-NR2 intermediate. The catalytic cycle proceeds without the need for external oxidants in a similar manner to the extensively studied palladium(0)-catalyzed C-H arylation reactions. The electron-deficient triarylphosphine ligand is crucial for this C(sp(3))-H amination reaction to occur.
A convergent and efficient preparation method of the photoaffinity 3-(4-alkoxyphenyl)-3-trifluoromethyldiazirine derivatives was established by direct introduction of the photoaffinity group utilizing the Mitsunobu reaction.
An intermolecular C(sp3)H amination using a Pd0/PAr3 catalyst was developed. The reaction begins with oxidative addition of R2NOBz to a Pd0/PAr3 catalyst and subsequent cleavage of a C(sp3)H bond by the generated PdNR2 intermediate. The catalytic cycle proceeds without the need for external oxidants in a similar manner to the extensively studied palladium(0)‐catalyzed CH arylation reactions. The electron‐deficient triarylphosphine ligand is crucial for this C(sp3)H amination reaction to occur.
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