General (hetero)polyaryl amine synthesis via multicomponent cycloaromatization of amines

Lebin Su; Jianyu Dong; Yang Shen; Shimin Xie; Shaofeng Wu; Neng Pan; Feng Liu; Qian Shang; Fangfang Cai; Tian-Bing Ren; Lin Yuan; Shuang-Feng Yin; Li-Biao Han; Yongbo Zhou

doi:10.1038/s41467-024-54190-5

General (hetero)polyaryl amine synthesis via multicomponent cycloaromatization of amines

Nat Commun. 2025 Jan 2;16(1):169. doi: 10.1038/s41467-024-54190-5.

Authors

Lebin Su^#^{1

2}, Jianyu Dong^#^{3

4}, Yang Shen^#¹, Shimin Xie^{1

2}, Shaofeng Wu¹, Neng Pan¹, Feng Liu¹, Qian Shang¹, Fangfang Cai¹, Tian-Bing Ren⁵, Lin Yuan¹, Shuang-Feng Yin^{6

7}, Li-Biao Han¹, Yongbo Zhou⁸

Affiliations

¹ State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, China.
² School of Physics and Chemistry, Hunan First Normal University, Changsha, China.
³ State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, China. [email protected].
⁴ School of Physics and Chemistry, Hunan First Normal University, Changsha, China. [email protected].
⁵ State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, China. [email protected].
⁶ State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, China. [email protected].
⁷ College of Materials Science and Engineering, Central South University of Forestry and Technology, Changsha, China. [email protected].
⁸ State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, China. [email protected].

^# Contributed equally.

Abstract

(Hetero)polyaryl amines are extensively prevalent in pharmaceuticals, fine chemicals, and materials but the intricate and varied nature of their structures severely restricts their synthesis. Here, we present a selective multicomponent cycloaromatization of structurally and functionally diverse amine substrates for the general and modular synthesis of (hetero)polyaryl amines through copper(I)-catalysis. This strategy directly constructs a remarkable range of amino group-functionalized (hetero)polyaryl frameworks (194 examples), including naphthalene, binaphthalene, phenanthren, benzothiophene, dibenzothiophene, benzofuran, dibenzofuran, quinoline, isoquinoline, quinazoline, and others, which are challenging or impossible to obtain using alternative methods. Copper(III)-acetylide species are involved in driving the exclusive 7-endo-dig cyclization, suppressing many side-reactions that are susceptible to occur. Due to the easy introduction of various functional units into heteropolyarylamines, multiple functionalized fluorescent dyes can be arbitrarily synthesized, which can serve as effective fluorescent probes for monitoring the pathological processes (e.g. chemotherapy-induced cell apoptosis) and studying the related disease mechanisms.