Recent Developments on Denitrogenative Functionalization of Benzotriazoles

Abstract

Benzotriazoles are employed as useful synthons in organic synthesis, and due to their unique structural motif, they are able to undergo denitrogenation during the construction of new bonds. Various methods for the functionalization of benzotriazoles as precursors of ­ortho-amino arenediazoniums have recently been developed that involve transition-metal-catalyzed coupling reactions, mainly via cyclization, borylation, alkenylation, alkylation, carbonylation and the formation of carbon–heteroatom bonds. In this short review, we primarily focus on the recent applications of benzotriazoles in organic chemistry that proceed via a denitrogenative process, and the mechanisms are also discussed.1 Introduction2 Common Synthetic Routes Allowing Easy Access to Benzotriazole Derivatives3 Formation of C–C Bonds3.1 Cyclization Reactions3.2 Arylation, Alkenylation, Alkylation and Carbonylation Reactions4 Carbon–Heteroatom Bond Formation5 Miscellaneous Denitrogenative Functionalization6 Conclusions and Future Perspectives

Synthetic Utility of N-Acylbenzotriazoles

“…Also, the benzotriazole ring cleavage (BtRC) methodology is well-established protocol that recently used in modern organic synthesis for an easy access of wide range of biologically relevant scaffolds. 1d 129 In addition to the versatile synthetic utilities of N -acylbenzotriazoles, this scaffold possesses some notable bioactivities and explored in medicinal chemistry. 130 The structures of some biologically potent N -acylbenzotriazoles are depicted in Figure 3 .…”

Advances in synthesis and biological activities of benzotriazole analogues: A micro review

“…If R = H, under basic conditions 1,3‐diphenyl‐triazene undergo the cis/trans isomerization, and the intramolecular amination is possible (Scheme 9) [28]. Thus, heating triazene ( 51 ) in the presence of Pd(OAc) 2 gave the direct amination product ( 53 ) in excellent yields.…”

“…If R = H, under basic conditions 1,3-diphenyltriazene undergo the cis/trans isomerization, and the intramolecular amination is possible (Scheme 9) [28]. Thus, heating triazene (51) in the presence of Pd(OAc) 2 gave the direct amination product (53) The scope of the protocol was explored by investigating a number of 3-methyl-1,3-diphenyltriazenes 51b-g under the optimal reaction conditions.…”

“…Vinod. K. Tiwari group [28] described various protocols for the functionalization of BTZs as precursors of ortho ‐amino arene diazoniums via transition‐metal‐catalyzed coupling reactions, mainly through borylation, cyclization, alkylation, carbonylation, alkenylation, and the development of carbon‐heteroatom bonds, with specific attention to applications of BTZs in organic chemistry that proceed via a denitrogenative process, and the mechanisms are also discussed.…”

Selective N–N or N–S bond cleavage of 1-trifluoromethyl benzotriazoles enables divergent synthesis of 1,2,4-benzotriazines and benzotriazoles

“…2 Even though great progress has been achieved in developing the denitrogenative functionalization of benzotriazoles (Fig. 1b), 15 the application of benzotriazoles as five-atom synthons in cycloaddition has rarely been reported. 16 As part of our ongoing research interest in developing novel methods to synthesize carbo- and heterocycles, 17 herein we disclose a base-promoted formal [5 + 1] cycloaddition of 1-trifluoromethyl benzotriazole and α-bromoacetophenone.…”