Cutting edge of diphenyl phosphorazidate (DPPA) as a synthetic reagent – A fifty-year odyssey

• Takayuki Shioiri^a
• Kotaro Ishihara^a
• and Masato Matsugi^a

• ^aFaculty of Agriculture, Meijo University, Shiogamaguchi, Tempaku, Nagoya 468- 8502, Japan

Recent advances of diphenyl phosphorazidate (DPPA) as a versatile synthetic reagent was described. It works as an azide anion equivalent, 1,3-dipole, an electrophile, and nitrene. Thus it can be conveniently used for amide synthesis, ester synthesis, modified Curtius reaction, phosphorylation, C-acylation, azide synthesis, Pummerer rearrangement, cycloadditions, diazotization, triazoline formation, Staudinger reaction, amidine and guanidine synthesis, C-H phosphorazidation, nitrene insertion, decarbonylation, etc. 1. Introduction 2. Preparation of DPPA 3. Amides and Lactams Synthesis 4. Esterification 5. The Modified Curtius Reaction 6. O- and N-Phosphorylations 7. Oxazoles Synthesis based on C-Acylation 8. Direct Conversion of Hydroxyl Groups to Azides 8.1 The Bose-Mitsunobu Azidation 8.2 The Merck Azidation 9. Pummerer Rearrangement of Sulfoxides 10. Cycloadditions 10.1 Reaction with Enamines 10.2 Synthesis of 1,2,3-Triazoles 10.3 Synthesis of Tetrazoles 11. Reaction with Organometallics 12. Staudinger Reaction 13. Synthesis of Amidines and Guanidines 14. C-H Phosphorazidation 15. As a Nitrene Source 16. Reaction with Silylene, Germylene, and Stanylene 17. Decarbonylation 18. Dimerization of Ynamides 19. Conclusion and Outlook.

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