In:
Angewandte Chemie, Wiley, Vol. 134, No. 52 ( 2022-12-23)
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.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v134.52
DOI:
10.1002/ange.202214507
Language:
English
Publisher:
Wiley
Publication Date:
2022
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