Photoinduced Tandem Three-Component Coupling of Propanedinitrile, 2,5-Dimethylhexa-2,4-diene, and Cyanoarenes

Autor:	Kazuhiko Mizuno, Keisuke Nakatani, Hajime Maeda, Maki Ohashi
Rok vydání:	2008
Předmět:	Addition reaction Reaction mechanism chemistry.chemical_compound Cascade reaction Nucleophile Chemistry Organic Chemistry Electrophilic aromatic substitution Photochemistry Bond cleavage Photoinduced electron transfer Malononitrile
Zdroj:	The Journal of Organic Chemistry. 73:8348-8351
ISSN:	1520-6904 0022-3263
DOI:	10.1021/jo801624q
Popis:	A tandem three-component coupling photoreaction proceeds upon photoirradiation of MeCN/H2O solutions containing propanedinitrile (1, malononitrile), 2,5-dimethylhexa-2,4-diene (2), and polycyanoarenes in the presence of phenanthrene and carbonate, leading to selective alpha-monoalkylation of 1. The reaction proceeds via photo-NOCAS (Nucleophile-Olefin Combination, Aromatic Substitution) type mechanism: nucleophilic attack of the anion of 1 to photogenerated 2(*+) is followed by ipso-substitution on the radical anion of the polycyanoarene. It advances under mild, safe, and environmentally friendly conditions such as proceeding at ambient temperature without metals and halogens, and in the presence of weak base. The reaction also represents a novel and metal-free cross-coupling reaction that leads to ipso-substitution on polycyanoarene via aryl-cyano bond cleavage. In addition, the reaction is a rare example of introducing carbon nucleophile in the photoinduced electron transfer reaction, except that of cyanide ion.
Databáze:	OpenAIRE
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