Taming Highly Unstable Radical Anions and 1,4-Organodilithiums by Flow Microreactors: Controlled Reductive Dimerization of Styrenes

[Image: see text] The reduction of styrenes with lithium arenide in a flow microreactor leads to the instantaneous generation of highly unstable radical anions that subsequently dimerize to yield the corresponding 1,4-organodilithiums. A flow reactor with fast mixing is essential for this reductive dimerization as the efficiency and selectivity are low under batch conditions. A series of styrenes undergo dimerization, and the resulting 1,4-organodilithiums are trapped with various electrophiles. Trapping with divalent electrophiles affords precursors for useful yet less accessible cyclic structures, for example, siloles from dichlorosilanes. Thus, we highlight the power of single-electron reduction of unsaturated compounds in flow microreactors for organic synthesis.