Diastereoselective singlet oxygen ene reaction (Schenck reaction) and diastereoselective epoxidations of heteroatom-substituted acyclic chiral olefins: a mechanistic comparison

The directing effect of several heteroatom substituents on the diastereoselectivity of the singlet oxygen ene reaction in acyclic, cbiral olefins is investigated to ascertain its role in the diastereoselective singlet oxygen ene reaction. Results indicate pronounced steering effects on the diastereoselectivity of oxygen transfer processes such as photooxygenation and epoxidation. Such effects are valuable for the rational design of stereocontrolled oxyfunctionalizations in 1O2, mCPBA and dioxiranes.