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Styrylsulfonates and ‐Sulfonamides through Pd‐Catalysed Matsuda–Heck Reactions of Vinylsulfonic Acid Derivatives and Arenediazonium Salts
Author(s) -
Schmidt Bernd,
Wolf Felix,
Brunner Heiko
Publication year - 2016
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201600469
Subject(s) - chemistry , heck reaction , salt (chemistry) , indole test , reactivity (psychology) , yield (engineering) , medicinal chemistry , olefin fiber , methyl acrylate , organic chemistry , acrylate , polymer chemistry , catalysis , palladium , medicine , materials science , alternative medicine , polymer , monomer , pathology , copolymer , metallurgy
Arene diazonium salts undergo Matsuda–Heck reactions with vinylsulfonates and ‐sulfonamides to give styrylsulfonic acid derivatives in high to excellent yields and with high to excellent selectivities. By quantifying the evolution of nitrogen over time in a gas‐meter apparatus, the reactivities of ethylvinylsulfonate and the benchmark olefin methyl acrylate were compared for an electron‐rich and an ‐deficient arene diazonium salt. Tertiary sulfonamides react in Matsuda–Heck couplings with high conversions, but require long reaction times, which prevents the determination of kinetic data through the measurement of nitrogen evolution. Secondary sulfonamides were found to be unreactive. From these results, the following order of reactivity could be deduced: H 2 C=CHCO 2 Me > H 2 C=CHSO 2 OEt > H 2 C=CHSO 2 N(Me)Bn >> H 2 C=CHSO 2 NHBn. Through the Matsuda–Heck coupling of 5‐indolyldiazonium salt and a tertiary vinylsulfonamide, the synthesis of the C‐5‐substituted indole part of the antimigraine drug naratriptan was accomplished in high yield.