Yuzo Fujiwara

Aromatic substitution of olefin—III : Reaction of styrene-palladium(II) chloride complex

Abstract trans-Stilbene derivatives have been obtained from a reaction of styrene-palladium (II) complex (1) with aromatic compounds in the presence of carboxylic acids. This novel method of synthesizing stilbene derivatives by substitution of an H atom on the double bond of the styrene of complex 1 is the first case of aromatic substitution of olefins. In a typical reaction, the complex 1 with benzene and acetic acid afforded trans-stilbene in a 26 % yield and a saturated acetate (13 %), and when sodium acetate was added, the yield was surprisingly increaased.

Aromatic substitution of olefin—VII : Reactions of lower olefins with benzene by palladium acetate☆

Abstract The phenylation of propylene, 1-butene, rans- and cis-butenes, and 1,3-butadiene with benzene was carried out in the presence of palladium acetate and acetic acid. It was concluded that, although the usual olefins predominantly undergo phenylation, an olefin which can easily form a π-allyl complex gives acetates as major products under the present reaction conditions.Abstract The phenylation of propylene, 1-butene, rans - and cis -butenes, and 1,3-butadiene with benzene was carried out in the presence of palladium acetate and acetic acid. It was concluded that, although the usual olefins predominantly undergo phenylation, an olefin which can easily form a π-allyl complex gives acetates as major products under the present reaction conditions.

Aromatic substitution of olefin—IX : Reactions of olefins containing a polar group with benzene

Abstract The phenylation of olefins containing a polar group was carried out in the presence of palladium acetate and acetic acid. The reaction mechanism is discussed.

Aromatic substitution of olefin—VIII : Substituent effects on the reactions of styrene with monosubstituted benzenes in the presence of palladium(II) salts

Abstract In the reactions of styrene with monosubstituted benzenes such as toluene, ethylbenzene, anisole or chlorobenzene in the presence of palladium(II) salts, the direction of substitution but not the reactivity is strongly influenced by the substituent on a benzene ring.

Aryl substitution of olefins. Reaction of σ-vinyl palladium(ii) with benzene or toluene: Evidence for the reaction mechanism

Abstract The reactions of σ-olefin-palladium(II)complexes with an aromatic compound such as benzene or toluene have been found to produce aryl-substituted olefins. This result provides support for a mechanism for the aromatic substitution of olefins in the presence of palladium acetate which involves a σ-bonded olefin-palladium(II) intermediate.