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O-Alkylation of Sulfinate Anion with a Palladium(II) Trimethylenemethane Intermediate Arising from [Pd{η3-CH2C(CH2Cl)CH2}(η5-C5R5)]

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journal contribution
posted on 08.01.1998, 00:00 by Saisuke Watanabe, Hideo Kurosawa
The reaction of [Pd{η3-CH2C(CH2Cl)CH2}(η5-C5R5)] (1) with NaSO2Ph initially affords the kinetically preferred O-alkylated complex [Pd{η3-CH2C(CH2OS(O)Ph)CH2}(η5-C5R5)] (2), which is subsequently transformed into the thermodynamically preferred S-alkylated complex [Pd{η3-CH2C(CH2SO2Ph)CH2}(η5-C5R5)] (3) and the bimolecular reaction product [Pd{η3-CH2C(CH2C5R5)CH2}(η5-C5R5)] (4). These reactions are rationalized by the intermediacy of a cationic trimethylenemethane−palladium complex.