Alkali metals, such as lithium and sodium, are naturally abundant elements, and their compounds are historically inexpensive and readily available. Due to these advantages, organic synthetic reactions utilizing alkali metals are among the most useful transformations, and countless studies have been reported to date. However, many of these classical reactions could entail practical problems, including inherently low selectivity and slow reaction rate, which in turn limits the substrate scope and require harsh conditions such as high temperature and pressure. Therefore, in this research, we have focused on the challenges remaining in classical reactions with over a century of history, specifically: (1) the alkylation of sugar derivatives, (2) the generation of benzylmetal species via the reductive cleavage of ether bonds, and (3) Kolbe-Schmitt reaction. This talk will feature three innovative methods that we have developed to solve these challenges, highlighting our latest unpublished and patent-pending results: lithium chelation-controlled highly site-selective sugar alkylation, rapid benzylsodium generation, and ambient pressure scalable Kolbe-Schmitt reaction.