Synthesis of Phosphorylated Indoles

Phosphorylated indoles are widely used not only in pharmaceutical chemistry, but also in the field of fine organic synthesis and materials science. In this regard, the synthesis of such compounds attracts great attention of researchers. This review presents advances in this area over the past 20 years. Particular attention is paid to the catalytic routes of synthesis corresponding to the current trends in organic chemistry.     

Conformational analysis of mono-and bis(dimethoxyphosphoryl)benzenes

Conformational analysis of mono-and bis(dimethoxyphosphoryl)benzenes with substituents in the benzene ring was performed by the method of dipole moments, IR spectroscopy, and quantum-chemical calculations (DFT B3LYP/6-31G*). Comparison of all calculated and experimental data shows that the compounds studied exist as equilibrium mixtures of conformers with preferred gg orientation of the phosphoryl and methoxy groups.     

Addition of Secondary Amines to Alkynephosphonates

Addition of secondary amines to diethyl alkynephosphonates, catalyzed by Cu(I) salts, proceeds regio- and stereospecifically and yields diethyl (E)-2-diethylaminooalkenephosphonates. The E configuration was established by analysis of the vicinal coupling constants between the phosphorus and carbon nuclei in the ¹³C NMR spectra of the reaction products and model compounds: ³ JPC is 6-10 Hz at the cis arrangement of the coupled nuclei and 16 Hz or higher at the trans arrangement. In all the diethyl diethylaminoalkenephosphonates obtained, ³ JPC is about 5 Hz, suggesting cis addition.     

Phosphorylation of Benzimidazole-2-thiones by Chloroethynylphosphonate

The reaction of chloroethynylphosphonates with N-substituted benzimidazole-2-thiones proceeded chemo- and regioselectively with the formation of cyclic zwitterions, namely alkyl (9H-benzo[4,5]imidazo[2,1-b]-thiazol-3-yl-4-ium)phosphonates. Chemo- and regioselective reaction of N-unsubstituted benzimidazole-2-thione with chloroethynylphosphonates led to the production of linear Z-1,2-bis(1H-benzimidazol-2-ylsulfanyl)-ethenylphosphonates.     

Synthesis and some transformations of dimethyl anabasylethynephosphonate

A new phosphorylated ynamine, dimethyl anabasylethynephosphonate, was synthesized by reaction of dimethyl chloroacetylenephosphonate with anabasine. Anabasylethynephosphonate obtained was shown to react under mild conditions with primary aromatic amines like p-chloroaniline, p-anisidine, and p-aminoacetophenone, whose pK _b values are in the range of 9–13, to form new asymmetrical phosphorylated acetamidines in high yields. Structure of the compounds obtained was proved by ¹H, ¹³C, and ³¹P NMR spectroscopy.     

Reaction of 2-[Aryl(alkyl)amino]malonates with Chloroethynylphosphonates

Russian Journal of General Chemistry - Preparative limitations of the reaction of chloroethynylphosphonates with 2-(alkylamino)malonates have been established. Unlike the reaction of...     

Synthesis of Symmetrical N -(Het)aryl- C -phosphonoacetamidines

A series of new symmetrical C-phosphonylated acetamidines was obtained by the reaction of diethyl chloroethynylphosphosphonate with a number of primary aromatic and heteroaromatic amines.