Synthesis of styrenes by palladium(II)-catalyzed vinylation of arylboronic acids and aryltrifluoroborates by using vinyl acetate.
One Heck of a reaction: Treatment of arylboronic acids or aryltrifluoroborates with vinyl acetate by using a palladium(II) catalyst gives the corresponding styrenes (see scheme). No palladium reoxidant is needed and the vinylation is performed under non-inert conditionsReactions of aromatic and heteroaromatic boronic acids or aryltrifluoroborate salts with vinyl acetate in the presence of a palladium(II) catalyst give the corresponding styrenes in good yields. This Heck reaction proceeds with microwave heating in less than 30 min at 140 degrees C in the absence of base and tolerates a variety of substituents. No palladium reoxidant is needed and the vinylation is performed under non-inert conditions. Mass spectrometry (electrospray ionization mass spectrometry (ESIMS) and tandem mass spectrometry (MS/MS)) was used to identify cationic palladium-containing complexes in ongoing reactions. The key intermediates that have been detected, together with experiments that used deuterated vinyl acetate, support the existence of catalytically active palladium hydride species, and that it is the arylation of ethylene, not vinyl acetate, which generates the styrene product. The mechanism of the reaction is discussed in terms of the palladium(II) intermediates mentioned above.
Lindh
Jonas
J
Department of Medicinal Chemistry, Organic Pharmaceutical Chemistry, Uppsala University, BMC, Box-574, SE-751 23 Uppsala, Sweden.
Sävmarker
Jonas
J
Nilsson
Peter
P
Sjöberg
Per J R
PJ
Larhed
Mats
M
D001897:Boronic Acids / Q000737:chemistry*; D002384:Catalysis; D010165:Palladium / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization; D013343:Styrenes / Q000138:chemical synthesis* / Q000737:chemistry; D014753:Vinyl Compounds / Q000737:chemistry*
D001897:Boronic Acids; D013343:Styrenes; D014753:Vinyl Compounds; D010165:Palladium; C011566:vinyl acetate