Allylic substitution of PhCH(OAc)CHdCHPh by CH 2 (COMe) 2 in a basic MeOH/H 2 O mixture could be achieved in the absence of a palladium catalyst and lead to a mixture of PhCH(CH(COMe) 2 )CHdCHPh and PhCH(OMe)CHdCHPh in 40% and 55% yields, respectively. The process is induced by water, and nucleophilic attack addition occurred on a stabilized carbocation as the intermediate. Addition of a catalytic amount of PdCl 2 (CH 3 CN) 2 did not accelerate the reaction but improved the selectivity, and PhCH(CH(COMe) 2 )CHdCHPh was then obtained in 92% yield while PhCH(OMe)-CHdCHPh was observed in trace amounts. An ESI-MS analysis of the reaction mixture led us to assume that a palladium acetylacetonate complex is involved in the formation of PhCH(CH(COMe) 2 )CHdCHPh.

In refluxing 1,2-dichloroethane under an argon atmosphere, 1-indanol led to a high yield of 1-indanone in the presence of sodium carbonate and catalytic amounts of (R 4 N) 2 PdCl 4 , while the use of PdCl 2 -(RCN) 2 as catalyst afforded di(1-indanyl) oxide quantitatively. These distinct reactive pathways would be due to the different electronic properties of the catalysts. The etherification reaction is limited to primary and secondary benzylic alcohols.

Under oxidative conditions that use an anionic palladium salt as catalyst, cis-endo-2,3-bis(hydroxymethyl)bicyclo[2.2.1]hept-5-ene affords the corresponding exo-lactol, while cis-endo-2,3-bis(hydroxymethyl)bicyclo[2.2.1]heptane provides the expected lactone. Mechanistic considerations explain how the presence of the CC bond blocks the oxidation at the lactol in the first case.