High-Yield Direct Synthesis of a New Class of Tertiary Organolithium Derivatives of Polycyclic Hydrocarbons

Article abstract of DOI:10.1021/jo00166a008

For the first time, 1- and 2-adamantyllithium, 1-diamantyllithium, 3,5,7-trimethyl-1-adamantyllithium, 1-twistyllithium, 3-methyl-7-noradamantyllithium, 1-triptycyllithium, and 3-homoadamantyllithium have been directly synthesized from the reaction of an organic halide and lithium metal.By use of certain experimental parameters, the phenomena at the metal-solution interface are controlled, thereby resulting in exceptionally high yields of this new class of organometallic compounds (>75percent, except in the case of 3-homoadamantyllithium).Competition between formation of the organometallic compound and formation of solvent-attack byproducts is determined by the degree of adsorption of the transient species (anion radical RX^-. or radical pair R..Li) generated at the metal surface during attack by the halogenated derivative.