Discovery and development of organo-<italic>di</italic>-lithio reagents: serendipity & persistence

Abstract

<p indent=0mm>In this account, we introduce the milestones during our scientific research since 1998, especially the serendipity and persistence in our continuous exploration into the chemistry of organo-<italic>di</italic>-lithio reagents (including but not limited to 1,4-dilithio-1,3-butadiene derivatives). Initially, the serendipity emerged from the discovery of the “cooperative effect” between organometallic reagents and Lewis acid. The effect of Lewis acid on organometallic transformations is summarized in three types: enhanced reactivity, enhanced selectivity, and changing the reaction pathway. Concurrently, during the mechanistic study of the “cooperative effect” between organometallic reagents and Lewis acid, the serendipity has led to the discovery of the intriguing reaction chemistry of organo-<italic>di</italic>-lithio reagents. The significance of its reactivity lies in the “cooperative effect” between two metal-carbon bonds, which distinguished it from the corresponding organo-<italic>mono</italic>-lithio reagents. The persistence drove us to further apply organo-<italic>di</italic>-lithio reagents in organic synthesis, leading to the development of four reaction patterns: intramolecular reactivity, intermolecular reactivity with organic substrates, transmetallation, and redox chemistry. Particularly, owing to the diverse characters of each individual metal, the transmetallation from organo-<italic>di</italic>-lithio reagents has enabled much richer reaction chemistry. Recently, our principal focus on the redox chemistry of organo-<italic>di</italic>-lithio reagents was also inspired by the initial serendipity and then led to innovative achievement following persistence.