Related Experiment Video
Updated: Aug 13, 2025

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI
Published on: November 22, 2016
Metal-Free S-Arylation of Phosphorothioate Diesters and Related Compounds with Diaryliodonium Salts
Sudeep Sarkar1,2, Marcin Kalek1
1Centre of New Technologies, University of Warsaw, Banacha 2C, 02-097 Warsaw, Poland.
Abstract:
We developed a direct metal-free S-arylation of phosphorothioate diesters using diaryliodonium salts. The method allows for the preparation under simple conditions of a broad range of S-aryl phosphorothioates, including complex molecules (e.g., dinucleotide or TADDOL derivatives), as well as other related organophosphorus compounds arylated at a chalcogen. The reaction proceeds with a full retention of the stereogenic center at the phosphorus atom, opening convenient access to P-chiral products. The mechanism of the reaction was established using DFT calculations.
Related Concept Videos
Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo,...
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
Diazonium Group Substitution: –OH and –H
Acidity of 1-Alkynes
The acidic strength of hydrocarbons follows the order: Alkynes > Alkenes > Alkanes. The strength of an acid is commonly expressed in units of pKa — the lower the pKa, the stronger the acid. Among the hydrocarbons, terminal alkynes have lower pKa values and are, therefore, more acidic. For example, the pKa values for ethane, ethene, and acetylene are 51, 44, and 25, respectively, as shown here.
Preparation and Reactions of Sulfides
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism

