Work

Sulfonyl-Directed Photoinduced Dehydro-Diels–Alder Reaction of Aryl Maleimides: Enabling Regioselective Naphthalene Synthesis

Year: 2026

Type: article

Abstract: Light-mediated intermolecular dehydro-Diels-Alder (DDA) reactions have emerged as a powerful strategy for constructing multisubstituted naphthalenesprivileged scaffolds found in natural products, pharmaceuticals, and functional materials. However, developing a general [4 + 2] cycloaddition system that accommodates electron-deficient dienes with both electron-rich and electron-deficient alkynes has remained challenging. Herein, we report a catalyst-free DDA reaction between sulfonyl-substituted aryl maleimides, serving as electron-deficient dienes, and alkynes under visible-light irradiation. By proceeding via a triplet intermediate manifold that bypasses conventional single-electron-transfer pathways and their redox matching constraints, this protocol enables efficient and regioselective access to diverse multisubstituted naphthalenes and exhibits broad compatibility with alkynes of varying electronic nature. Mechanistic studies reveal the essential dual role of the sulfonyl group in promoting the [4 + 2] cycloaddition with high chemoselectivity and facilitating the final aromatization step.

Source: JACS Au

DOI: 10.1021/jacsau.5c01485

Authors: Xian-Heng Song, Shan-Shui Meng, Yan-Jun Wan, Peng-Fei Wang, Albert Sun-Chi Chan, Ya-Jun Wang

Institutions: Zhejiang University of Technology, Sun Yat-sen University

Language: English

Topic: Radical Photochemical Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: gold

Estimated APC paid: $3,500