Allylic oxidations catalyzed by dirhodium caprolactamate via aqueous tert-butyl hydroperoxide: the role of the tert-butylperoxy radical.

ABSTRACT: Dirhodium(II) caprolactamate exhibits optimal efficiency for the production of the tert-butylperoxy radical, which is a selective reagent for hydrogen atom abstraction. These oxidation reactions occur with aqueous tert-butyl hydroperoxide (TBHP) without rapid hydrolysis of the caprolactamate ligands on dirhodium. Allylic oxidations of enones yield the corresponding enedione in moderate to high yields, and applications include allylic oxidations of steroidal enones. Although methylene oxidation to a ketone is more effective, methyl oxidation to a carboxylic acid can also be achieved. The superior efficiency of dirhodium(II) caprolactamate as a catalyst for allylic oxidations by TBHP (mol % of catalyst, % conversion) is described in comparative studies with other metal catalysts that are als

SUBMITTER: McLaughlin EC 

PROVIDER: S-EPMC2730049 | biostudies-literature | 2009 Jan

REPOSITORIES: biostudies-literature