Manganese(III) Acetate,CAN, andFe(III) Salts in Oxidative Radical Chemistry

Abstract

This article provides a broad overview of oxidative radical methods for the formation of CC bonds using manganese(III) acetate, cerium(IV) ammonium nitrate, and various iron(III) salts. The article begins with a discussion of the various general mechanisms encountered in oxidative radical chemistry and then provides an overview of inter and intramolecular CC bond‐forming reactions. The oxidative radical chemistry of β‐dicarbonyl and related compounds forms a major part of the article. Comparison of the three metals is made whenever possible as well as highlighting reactions which are specific to, or higher yielding with, one particular metal. The discussed synthetic methodologies are illustrated with examples of complex molecule synthesis.

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Manganese(III) Acetate-mediated Oxidative Cyclization of a-Methylstyrene and trans-Stilbene with b-Ketosulfones

“…Manganese(III) acetate has received considerable attention over the past several decades, and remains a useful tool for carbon-carbon bond formation [1,2,3,4]. Its specificity for carbonyl derivatives allows a wide variety of radical synthetic applications, leading to various structures like pyrrolidinones [5], γ-lactones [6,7], tetralins [8,9] or spirocyclic derivatives [10,11,12].…”

New Advances in Titanium-Mediated Free Radical Reactions

“…In the last decade, important improvements in this filed have been achieved by combining radical chemistry with transition-metal catalysis, due to the key role of transition metal complexes both in promoting and highly controlling sophisticated free-radical synthetic routes [ 4 , 5 , 6 , 7 ]. This approach has been adopted for different applications, ranging from oxidative [ 8 , 9 , 10 ] and reductive [ 11 ] radical processes to the selective C-C and C-N bond formation [ 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 ], passing through living polymerization [ 20 , 21 , 22 ].…”