Authors
Shi Tang, Longqing Yang, Fang Li, Zheng Jiang, Xiaohua Liu, Shunxi Dong, Xiaoming Feng
Published in
Angewandte Chemie (International ed. in English). Pages e7800916. Jul 07, 2026. Epub Jul 07, 2026.
Abstract
Catalytic dearomative photocycloaddition stands as one of the most powerful strategies for constructing highly complex, three-dimensional polycyclic scaffolds from readily accessible planar aromatic precursors. However, achieving asymmetric variants of these transformations with simple alkenes remains a formidable challenge, as it demands precise control over regio-, diastereo-, and enantioselectivity. Herein, we report asymmetric dearomatizing [2 + 2] and [4 + 2] photocycloadditions of 2-naphthalene derivatives by chiral terbium(III)/N,N'-dioxide complexes, wherein a pronounced ligand-acceleration effect is operative. The selectivity between the two pathways is governed by reaction temperature, alkene stoichiometry, and reaction time, thereby enabling the divergent synthesis of chiral cyclobutane-fused adducts (46 examples, up to 99% yield, > 19:1 dr, 99% ee) and bridged adducts (41 examples, up to 99% yield, up to 12:1 dr, 99% ee) with high efficiency. Notably, both cycloaddition manifolds accommodate terminal and internal olefins. Mechanistic investigations elucidate the origin of the ligand-acceleration effect and establish a kinetic basis for ortho-selectivity in the [2 + 2] pathway and a thermodynamic basis for para-selectivity in the [4 + 2] pathway. Density functional theory calculations further rationalize the competitive interplay between [2 + 2] and [4 + 2] cycloadditions and provide insight into the stereochemical outcome.
PMID:
42412057
Bibliographic data and abstract were imported from PubMed on 07 Jul 2026.
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