Atom Efficient Preparation of Zinc Selenates for the Synthesis of Selenol Esters under "On Water" Conditions.

Luca Sancineto,Gelson Perin,Eder Lenardao,Jaqueline Pinto Vargas,Bonifacio Monti,Massimiliano Arca,Vito Lippolis,Claudio Santi

doi:10.3390/molecules22060953

Abstract

We describe here an atom efficient procedure to prepare selenol esters in good to excellent yields by reacting [(PhSe)2Zn] or [(PhSe)2Zn]TMEDA with acyl chlorides under “on water” conditions. The method is applicable to a series of aromatic and aliphatic acyl chlorides and tolerates the presence of other functionalities in the starting material.

Highlights

Selenol esters are versatile tools in organic synthesis, once they can be converted to a sort of more complex molecules, acting as acyl-transfers, and in other important functional groups modifications [1]
During the reaction with acyl chlorides can be rationalized by Density Functional Theory (DFT) calculations demonstrating that the interactions between (PhSe)2 Zn species and the solvent units are remarkably stronger than those calculated between PhSeZnCl and PhSeZnBr and THF
After the removal of THF, the solid product obtained by the reduction of PhSeSePh with Zn in the presence of a catalytic amount of TFA (formally [(PhSe)2 Zn]) can be efficiently used for the synthesis of selenol esters starting from the corresponding acyl chlorides and using water as reaction medium

Summary

Introduction

Selenol esters are versatile tools in organic synthesis, once they can be converted to a sort of more complex molecules, acting as acyl-transfers, and in other important functional groups modifications [1]. Aromatic selenol esters, such as I, are stable liquid crystals with a large nematic mesophase range [2,3,4]. Selenol esters have gained even more importance, after the discovery that they can be used in native chemical ligation (NCL) reactions where the traditional thioester ligation chemistry is prohibitive [15,16]

Methods

Results

Conclusion