Search

Intramolecular oxy-palladation of hydroxy-alkenes leads to organo-Pd(II) intermediates which can be trapped by alkenes in chain extension by vinyl substitution; catalysis is efficient using a reoxidation system but the process is limited to substrates which cannot undergo β-hydride elimination from the organo-Pd(II) intermediate.

Alkenyl (phenyl) iodonium salts undergo cross-coupling with both vinyl and allyl trialkyltin compounds stereoselectively and at room temperature. Mild conditions are attributed to the high reactivity of Pd (0) toward the electrophilic hypervalent iodine molecule.

Using a coupling reaction between 8-iodo derivatives of O-TBDMS protected adenosine, 2′deoxyadenosine, 2′,3′-dideoxyadenosine and either vinyltributyltin or allyltributyltin with Pd(PPh 3 )4 catalysis, the corresponding 8-substituted nucleosides were obtained in excellent yields.

α-Trifluoromethanesulfonoxy ketones (α-keto triflates) have been synthesized under very mild conditions by the reaction of silyl enol ethers of ketones and trimethylsily trifluormethanesulfonate/iodosobenzene in dichloromethane.