Pro‐aromaticity Enabled Dealkenylative Functionalizations via Photo‐Excitation and Oxidation

• Published in: Chemistry : a European journal Vol. 29; no. 27; pp. e202203425 - n/a
• Main Authors: Chen, Si‐Cong, Zhu, Qi, Chen, Han, Chen, Zijing, Luo, Tuoping
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 11.05.2023; Wiley Subscription Services, Inc
• Subjects: Acylation; Alkylation; Aromaticity; Carbon; Chemistry; Chemistry, Multidisciplinary; Cycloaddition; C−C cleavage; dealkenylation; Excitation; Intermediates; Oxidation; photochemistry; Physical Sciences; radical reaction; Reagents; Science & Technology; Substrates; C-C cleavage; BIOMIMETIC SYNTHESIS; PHOTOREDOX; ALKYLATION; dealkenylation; radical reaction; oxidation; 4-ALKYL-1,4-DIHYDROPYRIDINES; CYANATION; DECARBOXYLATIVE ALKYNYLATION; photochemistry; CHEMISTRY; RADICALS; CARBOXYLIC-ACIDS; C−C cleavage
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202203425

A general and practical approach for diverse dealkenylative functionalization of olefin‐containing substrates has been developed through the one‐pot formation and utilization of pro‐aromatic 1,4‐dihydropyridazines using tetrazine as the key cycloaddition reagent. Triggered by either excitation or oxidation, the targeted C−C bonds in the 1,4‐dihydropyridazine intermediates could be readily cleaved to generate alkyl radicals for subsequent transformations. Diverse carbon‐carbon and carbon‐hetero bond forming protocols, including Giese‐type addition, hydrazination, borylation, Minisci‐type alkylation, copper‐catalyzed NH alkylation, acylation, alkynylation, cyanation, and azidation, are achieved in a highly modular fashion. Dealkenylative Giese‐type addition, hydrazination, borylation, Minisci‐type alkylation, copper‐catalyzed NH alkylation, acylation, alkynylation, cyanation, and azidation, have been achieved on olefin‐containing substrates in a one‐pot and highly modular fashion.