Palladium-catalyzed coupling of N-substituted isocyanide dichlorides with alkynyltin compounds: New synthesis of dialkynylketones

✍ Scribed by Yoshihiko Ito; Masahiko Inouye; Masahiro Murakami

• Publisher: Elsevier Science
• Year: 1988
• Tongue: French
• Weight: 197 KB
• Volume: 29
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)82873-7

✦ Synopsis

N-Substituted isocyanide dichlorides were coupled with alkynyltin compounds in the presence of palladium catalyst to produce N-substituted dialkynylimines, of which hydrolysis provides a convenient preparative method of dialkynylketones.

Synthetic utility of N-substituted isocyanide dichloride (l), which may be regarded to be a synthetic equivalent to phosgene, has been limited due to its relatively low reactivity. l) Nucleophilic substitutions of 1 with alcohols and amines have afforded N-substituted imino carbonate*) and urea3) derivatives, respectively. However, useful synthetic reactions of 1 with carbon nucleophiles have scarcely been reported. Herein, we wish to describe palladium-catalyzed coupling reactions of isocyanide dichloride (1) with alkynyltin (2) to produce N-substituted dialkynylimines (3), of which hydrolysis provides a convenient preparative method of dialkynylketones (4).4)