Anatomy of Long‐Lasting Love Affairs with Lithium Carbenoids: Past and Present Status and Future Prospects

After a long adolescence, the chemistry of lithium carbenoids has currently been entering its maturity bringing a dowry of a more in‐depth and less empirical knowledge of the structure and configurational stability of such double‐faced intermediates; this, thanks in particular to the synergistic and harmonic cooperation between calculations and the most modern NMR techniques now at our disposal. Such knowledge has stimulated the development of fruitful stereoselective applications in the field of organic synthesis, providing in addition a rationale to observed selectivities. Such aspects together with the role played by aggregation and solvation on the structure–reactivity relationship are highlighted throughout this Minireview with selected examples extracted from recent literature.