A Modular Approach to Arylazo-1,2,3-triazole Photoswitches

Abstract

Azoheteroarenes make up an emerging class of photoswitchable compounds with unique photophysical properties and advantages over traditional azobenzenes. Therefore, methods for synthesizing azoheteroarenes are highly desirable. Here, we utilize azide−alkyne click chemistry to access arylazo-1,2,3triazoles, a previously unexplored class of azoheteroarenes that exhibit high thermal stabilities and near-quantitative bidirectional photoconversion. Controlling the catalyst or 1,3-dipole grants access to both regioisomeric arylazotriazoles and arylazoisoxazoles, highlighting the versatility of our approach.

(Hetero)arylazo-1,2,3-triazoles: “Clicked” Photoswitches for Versatile Functionalization and Electronic Decoupling

“…Taking advantage of the orthogonality of the CuAAC click reaction, we designed a convenient one-pot approach to azo-1,2,3-triazoles where the formation of azide/alkyne and their cycloaddition could take place in the same reaction mixture, as shown in Scheme (see Supporting Information for experimental details) . This could also avoid the explosion risk of organic azides.…”

AgF‐Mediated Electrophilic Amination of Alkoxyarylsilanes with Azodicarboxylates

“…Other chemicals were obtained from commercial sources and used as received unless otherwise noted. Among the products, 3 a , 3 b , 3 f , 3 k , 3 m , 3 p , 3 q , 3 r , 4 a , 5 a are known compounds, [13b,19–23] the other compounds, 3 c , 3 e , 3 g , 3 h , 3 i , 3 j , 3 l , 3 n are new compounds and were fully characterized.…”

Copper-Catalyzed Alkynylation of Hydrazides: An Easy Access to Functionalized Azadipeptides

“…Among the potential coupling partners capable of transferring alkynes, HIR particularly attracted attention as they allowed the use of milder reaction conditions . While alkynylation using mononitrogen-based nucleophiles is well-established, only a few examples of the synthesis of ynehydrazides are reported . Initial attempts to alkynylate hydrazides with alkynyl HIR or bromalkynes required harsh conditions and/or afforded the products in poor yields. , To circumvent this issue, Batey and Beveridge followed an Umpolung strategy using azodicarboxylates as hydrazide precursors and acetylide nucleophiles (Scheme B) .…”