Heck–Matsuda Catalysis for the Synthesis of Spiro-Heterocycles from Diazonium Salts and via Tandem Diazotization from Anilines
Palavras-chave:
Heck-Matsuda, Organometallics, CatalysisResumo
The arenediazonium salt 1-(2-((2-methylenehex-5-en-1-yl)oxy)phenyl)-2-(tetrafluoro-l5-boraneyl)diazene (DZ1)
was synthesized from its corresponding aniline, 2-((2-methylenehex-5-en-1-yl)oxy)aniline (AN1), using HBF4 and tBuONO (tert
butyl nitrite) in ethanol. DZ1 was then subjected to a double Heck-Matsuda reaction using a palladium complex generated in
situ from [Pd(OAc)2] (10 mol%) and a chiral N,N-ligand (20 mol%), affording the spiro compounds 3'-methyl-2H
spiro[benzofuran-3,1'-cyclopentane]-3'-ene (major product 1) and 3'-methyl-2H-spiro[benzofuran-3,1'-cyclopentane]-2'-ene
(minor product 2) in 36% overall yield. In addition, a tandem catalysis approach was employed to access the same products
directly from the corresponding aniline in a one-pot process involving sequential diazotization and Heck-Matsuda reactions.
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