Local Desymmetrization through Diastereotopic Group Selection: An Enabling Strategy for Natural Product Synthesis

The application of desymmetrization strategies in chemical synthesis has allowed fundamentally new synthetic sequences that efficiently create dense and polyfunctional stereochemical arrays. Enantiotopic group discrimination has become a well‐established method of global desymmetrization, whereas the conceptually unique strategy of local desymmetrization by diastereotopic group discrimination has its own advantages. This microreview focuses on the application of local desymmetrization in natural product synthesis and places particular emphasis on the efficiency engendered by diastereotopic group discrimination. Local desymmetrization is subdivided into three distinct variants; examples under each paradigm are presented and compared.