Polyfunctionalized carbon frameworks containing 1,2-, 1,3-heteroatom-substituted fragments are ubiquitous in organic molecules. Construction of such motifs has been the central theme of organic synthesis throughout its history. Numerous methods have been developed to access such motifs, and the strategic usage of such reactions has historically been guided by polar retrosynthetic analysis (2e -disconnections). These classic methods can be broadly categorized into the functionalization of olefins and carbonyl compounds (Figure ). In the case of olefins, for example, Sharpless epoxidation/dihydroxylation/aminohydroxylation and related reactions can allow straightforward access to precursors that can then be converted to the desired target after further functionalization. The rich chemistry of carbonyl compounds encompasses a myriad of transformations ranging from the installation of heteroatoms in the adjacent position (e.g. Rubottom oxidation or asymmetric enamine chemistry) or classic C-C bond forming events such as aldol, Claisen condensation, pinacol coupling and Mannich reaction. The electrophilicity of carbonyl compounds allows for a combination with orthogonal olefin chemistry such as in the case of carbonyl allylation followed by oxidative cleavage.