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- Title
Diboron(4)‐Catalyzed Remote [3+2] Cycloaddition of Cyclopropanes via Dearomative/Rearomative Radical Transmission through Pyridine.
- Authors
Xu, Ming; Wang, Zhijun; Sun, Zhaohui; Ouyang, Yizhao; Ding, Zhengwei; Yu, Tao; Xu, Liang; Li, Pengfei
- Abstract
Ring structures such as pyridine, cyclopentane or their combinations are important motifs in bioactive molecules. In contrast to previous cycloaddition reactions that necessitated a directly bonded initiating functional group, this work demonstrated a novel through‐(hetero)arene radical transmission concept for selective activation of a remote bond. An efficient, metal‐free and atom‐economical [3+2] cycloaddition between 4‐pyridinyl cyclopropanes and alkenes or alkynes has been developed for modular synthesis of pyridine‐substituted cyclopentanes, cyclopentenes and bicyclo[2.1.1]hexanes that are difficult to access using known methods. This complexity‐building reaction was catalyzed by a very simple and inexpensive diboron(4) compound and took place via dearomative/rearomative processes. The substrate scope was broad and more than 100 new compounds were prepared in generally high yields. Mechanistic experiments and density function theory (DFT) investigation supported a radical relay catalytic cycle involving alkylidene dihydropyridine radical intermediates and boronyl radical transfer.
- Subjects
RING formation (Chemistry); PYRIDINE; CYCLOPENTENES; CYCLOPROPENE; DIHYDROPYRIDINE; CYCLOPROPANE derivatives; FUNCTIONAL groups; CYCLOPENTANE
- Publication
Angewandte Chemie, 2022, Vol 134, Issue 52, p1
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202214507