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

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Applications of Rozen’s Reagent in Oxygen-Transfer and C–H Activation Reactions
Synthesis ( IF 2.2 ) Pub Date : 2018-11-22 , DOI: 10.1055/s-0037-1609638
Kuldeep Singh ₁ , Kulbir Kulbir ₁ , Tarang Gupta ₂ , Rajneesh Kaur ₁ , Raman Singh ₁

Affiliation

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

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

中文翻译：

Rozen试剂在氧气转移和CH活化反应中的应用

致力于Shlomo Rozen教授在开发最佳氧气转移试剂方面的开拓性工作。

抽象的

Rozen的试剂（次氟酸-乙腈络合物，HOF·MeCN）是一种强大的非特异性氧气转移试剂，已成为氧化难以氧化的分子的行之有效的工具。它已被用于将氧气立即转移至官能团（例如烯烃，炔烃和芳烃），环氧化，醇，胺和炔烃的氧化，与氮，磷和含硫底物以及α-的氧转移反应羰基的羟基化。除了是潜在的绿色氧化剂外，该复合物还可以用于^18种O-标记和CH-H功能化策略。Rozen试剂在开发纳米材料和氧化膨胀石墨方面的最新用途表明了该试剂的巨大潜力。这些方面将在这篇评论中讨论。

1引言

2合成与物理性质

3安全与处理

4氧转移反应

4.1氧气转移的一般机制

4.2环氧化

4.3炔烃的氧化

4.4芳香醇和苯酚的氧化

4.5含氮化合物的氧化

4.6醛转化为腈

4.7醇和醚的氧化

4.8氧化含硫化合物