An efficient method for the synthesis
of C-phosphonoketenimines
through palladium-catalyzed migratory insertion of isocyanides has
been developed for the first time. This procedure tolerates wide functional
groups and has a good atom economy. Further transformations of the
products, which are useful building blocks for the β-aminophosphonates,
β-aminovinylphosphonates, and C-phosphorylated
tetrazoles, indicate potential synthetic utility.
A novel oxyfluorination of olefin reactions has been developed. The reactions involve a metal-free and green catalytic system for the synthesis of α-fluoroketones which is an important building block for organic synthesis. Moreover, this reaction system exhibits great functional group tolerance.
Chiral γ-phosphono-α-amino
acids play a crucial role
in inhibitors of natural enzymes, as well as agonists and antagonists
of metabotropic glutamate receptors. In this paper, an efficient and
general protocol for the construction of chiral γ-phosphono-α-amino
acids via Pd-catalyzed AQ-directed C(sp3)–H alkylation
of α-amino acid derivatives is developed. The reaction shows
reactivity between methylene C(sp3)–H bonds with
phosphonated alkyl iodides with high yields, enantioselectivity, and
diastereomeric ratios, which enables access to a wide range of challenging
and important γ-phosphono-α-amino acids in large scale.
Meanwhile, δ-phosphono-α-amino acid and δ-phosphono-propionic
acid derivatives can also be successfully obtained. The derivatization
reaction in the synthesis of l-AP4 and l-phosphinothricin
highlight the applicability of this method.
An efficient and practical method for the synthesis of α,α-difluoro-γ-aminophosphonates through photocatalyzed intermolecular aminodifluoromethylphosphonation of alkenes has been developed. In this reaction, difluoromethylphosphonate is used as an important fluorinated reagent. Furthermore, the mild reaction conditions, simple operation, and broad substrate scope make this protocol very practical and attractive. The derivatization reaction in the synthesis of difluoromethylphosphonated chiral binaphthylamine ligands and α,α-difluoro-γ-aminophosphoric acid highlight the applicability of this method.
A new strategy for the synthesis of chiral α-amino phosphonates by enantioselective C-H phosphonylation of allylamine with phosphite in the presence of a chiral Brønsted acid catalyst has been developed. This protocol successfully integrates direct C-H oxidation with asymmetric phosphonylation and exhibits high enantioselectivity.
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