Triflic Anhydride (Tf2O)-Activated Transformations of Amides, Sulfoxides and Phosphorus Oxides via Nucleophilic Trapping

Hai Huang; Jun Yong Kang

doi:10.1055/a-1679-8205

Synthesis, Table of Contents

Synthesis 2022; 54(05): 1157-1202
DOI: 10.1055/a-1679-8205

review

Triflic Anhydride (Tf₂O)-Activated Transformations of Amides, Sulfoxides and Phosphorus Oxides via Nucleophilic Trapping

Hai Huang

^aJiangsu Key Laboratory of Advanced Catalytic Materials & Technology, School of Petrochemical Engineering, Changzhou University, Changzhou 213164, P. R. of China

,

Jun Yong Kang∗

^bDepartment of Chemistry and Biochemistry, University of Nevada Las Vegas, 4505 South Maryland Parkway, Las Vegas, NV 89154-4003, USA

› Author Affiliations

Abstract

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Abstract

Trifluoromethanesulfonic anhydride (Tf₂O) is utilized as a strong electrophilic activator in a wide range of applications in synthetic organic chemistry, leading to the transient generation of a triflate intermediate. This versatile triflate intermediate undergoes nucleophilic trapping with diverse nucleophiles to yield novel compounds. In this review, we describe the features and applications of triflic anhydride in organic synthesis reported in the past decade, especially in amide, sulfoxide, and phosphorus oxide chemistry through electrophilic activation. A plausible mechanistic pathway for each important reaction is also discussed.

1 Introduction

2 Amide Chemistry

2.1 Carbon Nucleophiles

2.2 Hydrogen Nucleophiles

2.3 Nitrogen Nucleophiles

2.4 Oxygen and Sulfur Nucleophiles

2.5 hosphorus Nucleophiles

2.6 A Vilsmeier-Type Reagent

2.7 Umpolung Reactivity in Amides

3 Sulfoxide Chemistry

3.1 Oxygen Nucleophiles

3.2 Carbon Nucleophiles

3.3 Nitrogen Nucleophiles

3.4 Thionium Reagents

4 Phosphorus Chemistry

4.1 Hendrickson’s Reagent

4.2 Diaryl Phosphine Oxides

4.3 Phosphonates, Phosphates and Phosphinates

5 Conclusion and Outlook

Key words

electrophilic activation - amides - sulfoxides - phosphorus oxides - triflic anhydride - phosphonium triflate

Full Text

References

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