Allyl acetates electrolysis

The Pd(0)-catalyzed electrophilic reaction of allyl acetates (301) with elec-trochemically induced carbanions leading to (302) has been performed (Scheme 115) [436], The electrolysis is carried out in a DM F-Et4NCl04-(Pt) system in the presence of the active hydrogen compound, Ph3P, and Pd(II)(PhCN)2Cl2 at a current density of 0.26 A dm and the allyl acetate (301). 

An alternative approach to the commonly utilized cleavage of allylic isoprenoid compounds (Scheme 16) using attack of +2e in place of H at a Pd° ir-allyl complex also requires a catalyst addition.Electrolysis of allylic acetates with Pb cathode and Pt anode in the presence of Pd(PPh3)4 in MeCN, gave moderate yields of the inner alkenes from both terminal and inner acetates (equations 92 and 93). Control of the regioselectivity was clearly dictated by the attack of H+ from the less-hindered side of the allylic carbanions. 

The allyl diacetate [9] can be obtained in 80% yield and in a very simple reaction by electrolysis of methyl konjuenate in an undivided cell in acetic acid as solvent (see above). It was therefore of great interest to determine whether this readily available acetate also reacts with nucleophiles under palladium(0)-catalysis. Indeed, [9] can be joined to carbon nucleophiles in moderate to good yield to form the conjugates [42] and [43] (Eq. 21). A disubstitution could not be enforced, however, despite the use of a fivefold excess of the nucleophile. 

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