Application of Organic Azides for the Synthesis of Nitrogen-Containing Molecules

Abstract

In this account, recent advances made on the reactions of several types of organic azides, such as vinyl azides, cyclic 2-azido alcohols, a-azido carbonyl compounds, towards the synthesis of nitrogen-containing molecules are described. 1 Introduction 2 Chemistry of Vinyl Azides 2.1 Thermal [3+2]-Annulation of Vinyl Azides with 1,3-Dicarbonyl Compounds 2.2 Manganese(III)-Catalyzed Formal [3+2]-Annulation with 1,3-Dicarbonyl Compounds 2.3 Manganese(III)-Mediated/Catalyzed Formal [3+3]-Annulation with Cyclopropanols 2.4 Synthesis of Isoquinolines from a-Aryl-Substituted Vinyl Azides and Internal Alkynes by Rhodium-Copper Bimetallic Cooperation 3 Chemistry of Cyclic 2-Azido Alcohols 3.1 Manganese(III)-Catalyzed Ring Expansion of 2-Azidocyclobutanols 3.2 Palladium(II)-Catalyzed Ring Expansion of Cyclic 2-Azido Alcohols 4 Chemistry of a-Azido Carbonyl Compounds 4.1 Orthogonal Synthesis of Isoindole and Isoquinoline Derivatives 4.2 Generation of Iminylcopper Species and Their Catalytic Carbon-Carbon Bond Cleavage under an Oxygen Atmosphere 4.3 Copper(II)-Catalyzed Aerobic Synthesis of Azaspirocyclohexadienones 5 Conclusion

Comparative Study of the Catalytic Amination of Benzylic C–H Bonds Promoted by Ru(TPP)(py)2 and Ru(TPP)(CO)

“…Unfortunately, we did not observe the coordination of one ArN 3 ligand to the metal centre yielding 5 or the mono-imido derivative 6. The NMR analysis of the crude reaction product revealed the presence of an equimolar mixture of Ru(TPP)(py) 2 (2) and bis-imido complex Ru(TPP)(NAr) 2 (7). This suggests that, even if compounds 5 and 6 are momentarily formed, they are too elusive to be experimentally detected, most likely because 7 is quickly formed as the thermodynamically stable product (Scheme 1, path c).…”

Reactivities of vinyl azides and their recent applications in nitrogen heterocycle synthesis

“…2 However, vinyl azides have been regarded as “sleepers” among the reactive azido species, and they drew little attention over the course of the last century. Until recently, efforts to employ vinyl azides have focused largely on their use as a pivotal three-atom synthon for the formation of diverse N -heterocycles.…”

“…11 Even this seemingly large topic encompasses a relatively small subset of the types of reactions open to vinyl azides. 2,11 The present Review, therefore, is intended to enumerate and classify the types of possible reactive intermediates that can be generated from vinyl azides under different reaction conditions. Furthermore, this Review highlights how these diverse reaction pathways make vinyl azides outstanding building blocks in N -heterocycle synthesis.…”

Vinyl‐ und Alkinyl‐Azide: altbekannte Intermediate im Fokus moderner Synthesemethoden

“…1-Azidoalkene (1) dienen (in Form von Azidovinylidenen) als Vorläufer für 1-Azidoalkine (21). B. zur Synthese von Lactamen und azabicyclischen Systemen (Mn III ), [3] zur Synthese von Isochinolinen (Rh-Cu) [4] und Indolen (Rh 2 II ) [5] bekannt. Vinylazide werden in Heterocyclensynthesen meist als Syntheseäquivalent für Vinylnitrene (2 a) oder Azirine (2 b) genutzt; die Bezeichnung Diazoenamine trägt so der leichten Überführbarkeit der Verbindungen 1 in 2 a oder 2 b durch Erwärmen oder Photolyse am deutlichsten Rechnung (Schema 1).…”

“…Des Weiteren sind ähnliche Protokolle unter Metallkatalyse z. B. zur Synthese von Lactamen und azabicyclischen Systemen (Mn III ), [3] zur Synthese von Isochinolinen (Rh-Cu) [4] und Indolen (Rh 2 II ) [5] bekannt. Unter leichter Veränderung der Reaktionsbedingungen (niedrigere Temperatur, Base) kann der Zerfall der Azid-Einheit zu 2 a auch verhindert werden.…”