Oxygen-Bearing Lithium Compounds in Modern Synthesis

This chapter addresses the genesis, reactivity and applications of oxygen-bearing lithium compounds in organic synthesis, focusing in particular on the most recent inspiring contributions in this area over the past decade. Key selected examples dealing with stereochemical aspects of asymmetric transformations and natural product synthesis are herein presented, and special attention is also deserved to mechanistic, structural, and spectroscopic studies with the aim of providing readers, wherever applicable, information about the structure-reactivity relationship which is central to the organolithium field. The chapter begins with an overview of α-lithiated oxygen-substituted compounds split into two subsections: acyclic (nonstabilized and dipole-stabilized) and cyclic α-alkoxy organolithiums, discussing their chemical and configurational stability as well as synthetic applications. Next, a section describes the effectiveness and advantages of ortho-lithiation for regioselective functionalization/transformations of oxygen-bearing aromatic compounds. Finally, new synthetic opportunities associated with remote or "through-space"-induced lithiation are also highlighted. The chapter concludes with an outlook section concentrating on new directions and opportunities in the area of oxygenated compounds which, hopefully, may contribute to the future growth of the field.