First Examples of the Atherton–Todd‐Like Reaction in the Absence of Bases

Abstract

Oxidative cross‐coupling between secondary phosphine chalcogenides and alcohols or phenols proceeds in CCl4 medium at 80–82°C to afford phosphinoсhalcogenоic O‐esters in up to 92% yield. These couplings represent first examples of the Atherton–Todd‐like reaction occurring in the absence of bases.

Lewis-acid-catalyzed phosphorylation of alcohols

“…Recently, a novel Brønsted-acid-catalyzed phosphorylation of o -hydroxybenzyl alcohol has been developed—leading to the synthesis of diphenylphosphonates from trialkylphosphites serving as starting materials and achieved using the phosphate-Michael addition reaction 14 ( Scheme 1d ). In addition, synthetic chemists have made remarkable progress in investigating methods for forming P–O bonds between P sources and alcohols in recent years, with examples of these methods including, the nucleophilic substitution reaction, 15 Atherton–Todd reaction, 16 cross-dehydrogenative coupling reaction 17 and electrophile reaction. 18 Our group focuses on the phosphorylation of ketones or aldehydes via the phospha-aldol-elimination (PAE) reaction catalyzed by Lewis acid or Brønsted acid.…”

Synthesis, Molecular and Crystal Structures of Tetraethyl 1,3-Phenylenebis (Phosphoramidate) and Tetrapropyl 1,3-Phenylenebis (Phosphoramidate)

“…Малоизученными остаются фосфорорганические производные диаминов ароматического ряда, имеющих различные заместители как в ароматическом цикле, так и у атома фосфора (Ou, 2020;Trofimov, 2015) . В литературе практически отсутствуют данные о фосфорилировании мета-фенилендиамина.…”

Low-Valent-Tungsten-Catalyzed Aerobic Oxidative Cross-Dehydrogenative Coupling Reaction

“…Accordingly, several synthetic routes for the construction of thiophosphates have been well established in recent years (Scheme 1) [7][8][9]. These methods could be divided into four categories: (a) direct nucleophilic substitution of pre-functionalized S-X or P(O)-X 2 of 9 reagents; [10][11][12] (b) the Atherton-Todd reaction with the utilization of polyhaloalkanes as both the reagent and solvent; [13][14][15][16] and (c) cross-dehydrogenative couplings of P-H bond and S-H bond [17][18][19][20][21][22][23]. Among these methods, the direct phosphorylation of thiols is atom-and step-economic, practical, and environmentally friendly.…”