Guanidines in organic synthesis

Guanidine is categorized as an organic superbase, yet its synthetic application is immature despite its wide potential utility. The role of guanidine in organic synthesis, including asymmetric reactions, is discussed herein. 1 Introduction 2 TMG and Its Analogues in Organic Synthesis 2.1 Alkylation of Carboxylic Acids 2.2 Barton's Bases 2.3 Baylis-Hillman Reactions 2.4 Bismuth-Mediated Reactions 2.5 Cyclopropanations 2.6 Horner-Emmons Reactions 2.7 Ionic Liquids 2.8 Michael Reactions 2.9 Nitroaldol (Henry) Reactions 2.10 Nucleophilic Reactions with Thiols 2.11 Palladium-Catalyzed Reactions 2.12 Silylation of Alcohols 2.13 Supported Guanidines 2.14 TMG Azides 3 Applications toward Asymmetric Synthesis 3.1 Alkylation of Carboxylic Acids 3.2 Alkylation of Schiff Bases 3.3 Azidations 3.4 Michael Reactions 3.5 Nitroaldol (Henry) Reactions 3.6 Nucleophilic Epoxidations 3.7 Silylation of Alcohols 3.8 Strecker Reactions 3.9 TMS Cyanations 3.10 Others 4 Conclusion.