Deoxydichlorination of aldehydes catalyzed by Diphenyl sulfoxide

I A Gorbunova,S A Shipilovskikh,D A Shipilovskikh

doi:10.15826/chimtech.2021.8.4.08

I A Gorbunova, S A Shipilovskikh + Show 1 more

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https://doi.org/10.15826/chimtech.2021.8.4.08

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Abstract

The diphenyl sulfoxide-catalyzed conversion of aldehydes to 1,1-dichlorides is reported. The reaction proceeds via a sulfurous (IV)-catalysis manifold in which diphenyl sulfoxide turnover is achieved using oxalyl chloride as a consumable reagent.

Highlights

Nucleophilic substitutions SN are general chemical transformations, as they allow, for example, strategic building of C–Cl, C–O, C–N and C–C bonds [1,2,3,4,5,6,7,8,9,10]
Reaction progress was monitored by GC/MS analysis and thin layer chromatography (TLC) on aluminum backed plates with Merck Kiesel 60 F254 silica gel
Diphenyl sulfoxide (Ph2SO) (40 mg, 0.2 mmol, 0.1 equiv, 10 mol.%) and aldehyde 1 (2 mmol, 1 equiv) were dissolved in 15 mL of anhydrous toluene in a 25 mL round bottom flask equipped with a magnetic stirring bar

Summary

Introduction

Nucleophilic substitutions SN are general chemical transformations, as they allow, for example, strategic building of C–Cl, C–O, C–N and C–C bonds [1,2,3,4,5,6,7,8,9,10]. Geminal dihalides, especially dichlorides, are important intermediates in chemical synthesis, and the traditional synthesis protocols are often limited in terms of cost efficiency and waste balance [11, 12]. Research in this area is at an early stage in the study of such catalytic reaction. Dichlorides – important class of intermediates in organic synthesis. They were used for alkenylation of carbonyl compounds [15, 16], cyclopropanation and epoxidation [17,18,19], dimerization [20, 21] and others [22,23,24,25]. Geminal dichlorides are encountered as structural motifs in polyhalogenated natural products [26, 27] (Fig. 1)

Experimental

General method for synthesis of dichlorides from aldehyde

Results and discussion

Conclusions