期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 61, 期 12, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202214507
关键词
Boron Catalysis; Cycloaddition; Metal-Free; Pyridine; Radical Transmission
资金
- NSFC
- Natural Science Basic Research Plan of Shaanxi Province
- [21971202]
- [22171218]
- [2020JC-08]
This study developed a novel method for selective activation of a remote bond using a through-(hetero)arene radical transmission concept. By a metal-free [3+2] cycloaddition reaction, pyridine-substituted cyclopentanes, cyclopentenes, and bicyclo[2.1.1]hexanes that are difficult to access using known methods were synthesized. The reaction was catalyzed by a simple and inexpensive diboron(4) compound and proceeded via dearomative/rearomative processes.
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.
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