A novel three-component reaction between isocyanides, alcohols or thiols and elemental sulfur: a mild, catalyst-free approach towards O-thiocarbamates and dithiocarbamates.

András György Németh,György Miklós Keserű,Péter Ábrányi-Balogh

doi:10.3762/bjoc.15.155

András György Németh, György Miklós Keserű + Show 1 more

Open Access

https://doi.org/10.3762/bjoc.15.155

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Journal: Beilstein journal of organic chemistry	Publication Date: Jul 10, 2019
Citations: 21	License type: CC BY 4.0

Abstract

A new multicomponent reaction has been developed between isocyanides, sulfur and alcohols or thiols under mild reaction conditions to afford O-thiocarbamates and dithiocarbamates in moderate to good yields. The one-pot reaction cascade involves the formation of an isothiocyanate intermediate, thus a catalyst-free synthesis of isothiocyanates, as valuable building blocks from isocyanides and sulfur is proposed, as well. The synthetic procedure suits the demand of a modern organic chemist, as it tolerates a wide range of functional groups, it is atom economic and easily scalable.

Highlights

O-Thiocarbamates belong to a class of important biologically active molecules, used mainly as fungicides [1,2,3] in agricultural and pharmaceutical fields
The dithiocarbamate structural moiety can be found in biologically active molecules widely applied as fungicides, herbicides, pesticides [21,22,23,24,25] and in some cases as enzyme inhibitors [26] or antitumor agents [27]
As a continuation of our interest in the development of multicomponent reactions [85,86,87] and reactions involving sulfur [88], we describe a novel synthesis of O-thiocarbamates and dithiocarbamates via a three-component reaction of elemental sulfur, isocyanides and alcohols or thiols (Scheme 1)

Summary

Introduction

O-Thiocarbamates belong to a class of important biologically active molecules, used mainly as fungicides [1,2,3] in agricultural and pharmaceutical fields. All the previously reported methods for the synthesis of O-thiocarbamates, dithiocarbamates and isothiocyanates start from toxic and/or unstable reagents, generate halogen waste or have narrow functional group tolerance. As a continuation of our interest in the development of multicomponent reactions [85,86,87] and reactions involving sulfur [88], we describe a novel synthesis of O-thiocarbamates and dithiocarbamates via a three-component reaction of elemental sulfur, isocyanides and alcohols or thiols (Scheme 1).

Results

Conclusion