Applications of Rozen’s Reagent in Oxygen-Transfer and C–H Activation Reactions

Dedicated to Professor Shlomo Rozen for his pioneering work in developing the best oxygen-transfer reagent.

Abstract

Rozen’s reagent (hypofluorous acid–acetonitrile complex, HOF·MeCN) is a robust nonspecific oxygen-transfer reagent and became a proven tool for the oxidation of difficult-to-oxidize molecules. It has been applied to instant oxygen transfers to functional groups such as alkenes, alkynes, and aromatic hydrocarbons, epoxidation, oxidation of alcohols, amines, and alkynes, oxygen-transfer reactions with nitrogen, phosphorus, and sulfur-containing substrates, and α-hydroxylation of carbonyl groups. Apart from being a potential green oxidizing agent, the complex has applications in ¹⁸O-labeling and C–H functionalization strategies. Recent uses of Rozen’s reagent in developing nanomaterials and oxidized expanded graphite indicate the enormous potential of the reagent. These aspects are discussed in this review.

1 Introduction

2 Synthesis and Physical Properties

3 Safety and Handling

4 Oxygen-Transfer Reactions

4.1 General Mechanism of Oxygen Transfer

4.2 Epoxidation

4.3 Oxidation of Alkynes

4.4 Oxidation of Aromatic Alcohols and Phenols

4.5 Oxidation of Nitrogen-Containing Compounds

4.6 Conversion of Aldehydes into Nitriles

4.7 Oxidation of Alcohols and Ethers

4.8 Oxidation of Sulfur-Containing Compounds

4.9 Oxygen-Transfer Reaction with Phosphine, Phosphite, and Phosphinite Compounds

5 C–H Activation Reactions

5.1 Hydroxylation of Nonactivated Tertiary Saturated Carbon Center

5.2 Hydroxylation of Aromatic Carbon Center

5.3 α-Hydroxylation of Carbonyl Group

5.4 Activation of α-Hydrogens of α-Amino Acids

6 Other Uses

7 Green Chemistry and Rozen’s Reagent

8 Experimental Problems

9 Further Applications

10 Conclusions

Key words

Rozen’s reagent - Rozen oxidation - C–H functionalization - oxygen-transfer reaction - ¹⁸O labeling - hypofluorous acid–acetonitrile complex - green synthesis

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