Rapid access to polycyclic N-heteroarenes from unactivated, simple azines via a base-promoted Minisci-type annulation

Conventional synthetic methods to yield polycyclic heteroarenes have largely relied on metal-mediated arylation reactions requiring pre-functionalised substrates. However, the functionalisation of unactivated azines has been restricted because of their intrinsic low reactivity. Herein, we report a t...

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Bibliographic Details
Published in:Nature communications 2022-05, Vol.13 (1), p.2421-2421, Article 2421
Main Authors: Lee, Jae Bin, Kim, Gun Ha, Jeon, Ji Hwan, Jeong, Seo Yeong, Lee, Soochan, Park, Jaehyun, Lee, Doyoung, Kwon, Youngkook, Seo, Jeong Kon, Chun, Joong-Hyun, Kang, Seok Ju, Choe, Wonyoung, Rohde, Jan-Uwe, Hong, Sung You
Format: Article
Language:English
Subjects:
140/131
140/58
639/638/403/933
639/638/77/889
Aromatic compounds
Azines
Chemical reactions
Chemistry
Electrochemistry
Electron paramagnetic resonance
Electron spin resonance
Electrons
Humanities and Social Sciences
Methods
multidisciplinary
Oxidation
Relay
Salts
Science
Science (multidisciplinary)
Substrates
Transition metals
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Summary:Conventional synthetic methods to yield polycyclic heteroarenes have largely relied on metal-mediated arylation reactions requiring pre-functionalised substrates. However, the functionalisation of unactivated azines has been restricted because of their intrinsic low reactivity. Herein, we report a transition-metal-free, radical relay π-extension approach to produce N-doped polycyclic aromatic compounds directly from simple azines and cyclic iodonium salts. Mechanistic and electron paramagnetic resonance studies provide evidence for the in situ generation of organic electron donors, while chemical trapping and electrochemical experiments implicate an iodanyl radical intermediate serving as a formal biaryl radical equivalent. This intermediate, formed by one-electron reduction of the cyclic iodonium salt, acts as the key intermediate driving the Minisci-type arylation reaction. The synthetic utility of this radical-based annulative π-extension method is highlighted by the preparation of an N-doped heptacyclic nanographene fragment through fourfold C–H arylation. The functionalisation of unactivated azines has been restricted because of their intrinsic low reactivity. Here the authors show a transition-metal-free, radical relay π-extension approach to produce N-doped polycyclic aromatic compounds directly from simple azines and cyclic iodonium salts.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-022-30086-0