Enecarbamates as Selective Substrates in Oxidations: Chiral-Auxiliary-Controlled Mode Selectivity and Diastereoselectivity in the [2+2] Cycloaddition and Ene Reaction of Singlet Oxygen and in the Epoxidation by DMD and <i>m</i>CPBA

The stereochemical course of the oxidation of chiral oxazolidinone-substituted enecarbamates has been studied for singlet oxygen (1O2), dimethyldioxirane (DMD), and m-chloroperbenzoic acid (mCPBA) by examining of the special structural and stereoelectronic features of the enecarbamates. Valuable mechanistic insight into these selective oxidations is gained. Whereas the R1 substituent on the chiral auxiliary is responsible for the steric shielding of the double bond and determines the sense of the π-facial diastereoselectivity, structural characteristic such as the Z/E configuration and the nature of the R2 group on the double bond are responsible for the extent of the diastereoselectivity. Stereoelectronic steering by the vinylic nitrogen functionality controls the mode selectivity (ene reaction vs [2+2] cycloaddition) in the case of 1O2.