Radical addition of ketones and cyanide to olefinsviaacid catalyzed formation of intermediate alkenyl peroxides

Wen Shao,Martin Breugst,Marcel Lux,Martin Klussmann

doi:10.1039/c9qo00447e

Abstract

γ-Cyanoketones are formed by double radical addition from olefins, ketones and sulfonyl cyanidesviareactive alkenyl peroxide intermediates.

Highlights

Radical addition reactions enable the double functionalization of olefins with heteroatom- and carbon-residues, much effort is put into their development.[1]
We have recently developed a method for the acid-catalyzed generation of radicals from ketones and hydroperoxides via the intermediate formation of alkenyl peroxides 1 (Scheme 1a).[2]
We were interested to extend the radical addition of ketones via this mechanism to the twofold addition of carbon-radicals instead of the carboperoxidation as in the synthesis of 2

Summary

Introduction

Radical addition reactions enable the double functionalization of olefins with heteroatom- and carbon-residues, much effort is put into their development.[1]. The generation of radicals in the α-position of ketones can be achieved by alternative means,[5] but often it is only effective with 1,3-dicarbonyl compounds,[6] at temperatures above 100 °C,7 with α-bromo-ketones as substrates[8] and larger amounts of metal reagents,[9] respectively. Their formation via alkenyl peroxides (1) by condensation with hydroperoxides, on the other hand, is effective with plain ketones and only requires simple acids as catalysts. Adding ketone and cyanide radicals to an olefin could allow the synthesis of γ-cyanoketones not accessible by the aforementioned methods

Results and discussion

Conclusions

Conflicts of interest