ChemInform Abstract: PHOSPHORYLATION OF INDOLES BY AMIDOPHOSPHITES

Abstract

Die Phosphorylierung des Indols (I) mit den Phosphorverbindungen (II) liefert das in 1‐Stellung substituierte Derivat (III).

Amides of Trivalent Phosphorus Acids as Phosphorylating Reagents for Proton-Donating Nucleophiles

“…Let us turn to C-phosphorylation of organic compounds by ATPA. This possibility has already been noted in relation to phosphorylation of hydrogen cyanide 695 and indole . Azaphosphole condensation is a more interesting example of this reaction (Scheme )…”

“…Transamidation can also be used to synthesize complex asymmetrical systems including phosphorylated ethyleneimines ,, and glucosylamines. , In some cases, transamidation can be supplemented by C-phosphorylation, as in the experiments with indole presented in Scheme 90 …”

“…506,507 In some cases, transamidation can be supplemented by C-phosphorylation, as in the experiments with indole presented in Scheme 90. 508 3-Mercaptoindole 509 and 3-hydroxymethylindole 510 are phosphorylated either at nitrogen or at sulfur (oxygen), depending on the reaction conditions.…”

“…This possibility has already been noted in relation to phosphorylation of hydrogen cyanide 695 and indole. 508 Azaphosphole condensation is a more interesting example of this reaction (Scheme 158). 706 Isomerization of phosphorylated vinylamines consisting in the replacement of the amido group by a hydrocarbon radical with migration of a hydrogen atom from carbon to nitrogen also deserves attention.…”

N → C3 migration of dichlorophosphino group in the phosphorylation of N‐unsubstituted indole with phosphorus trichloride

“…It has been known that direct phosphorylation of unsubstituted indole with phosphorus acid halides proceeds mostly at the nitro- gen atom [3,4]. However, when using amidophosphorous esters as phosphorylating agents, initially formed N-phosphorylated derivatives rearrange intramolecularly to C 3 -substituted products [5] under the catalytic action of amine hydrochlorides present in the reaction mixture. A similar N → C 3 sigmatropic rearrangement of phosphorylated indoles occurs in the hydrolysis and alcoholysis of N-indolylamidophosphite with respective equimolar amounts of water or alcohol [6].…”