Photoinduced Pd-catalyzed desaturation of silyl ethers

This thesis describes the development of site-selective remote C(sp3)-H desaturation and alkenylation reactions of aliphatic systems involving the novel hybrid Pd-radical species. This new mode of Pd-catalyzed reactions takes an advantage of a powerful radical process for selective remote C(sp3)-H activation, a hydrogen atom transfer (HAT) process; and synergistically combines that with versatile Pd-catalyzed reactions at the remote C(sp3)-H site. The combination of these two chemical universes has led to an increased efficiency, generality, and selectivity for remote C(sp3)-H desaturation and alkenylation reactions. The overall transformation allows for a general conversion of readily available aliphatic alcohols and amines into synthetically useful enols/enamines, allylic- and homoallylic alcohols/amines. Furthermore, these novel transformations proceeded under mild, visible light-induced conditions at room temperature without the use of exogenous photosensitizers or external oxidants. The selectivity of remote C(sp3)-H functionalization sites is controllable/predictable by the employment of easily installable/removable auxiliaries, which represents the generality of this approaches. It is anticipated that these novel transformations would find broad application in synthesis; and this new strategy could lead to a new avenue for site-selective remote C(sp3)-H functionalization reactions.