Polyyne synthesis using carbene/carbenoid rearrangements

Rearrangement of a carbene/carbenoid intermediate to form an acetylene moiety, known as the Fritsch-Buttenberg-Wiechell (FBW) rearrangement, was developed for the formation of polyynes and polyyne frameworks within highly conjugated organic materials. Necessary precursors can be prepared through formation of an alkynyl ketone, followed by dibromoolefination under Corey-Fuchs conditions. The carbenoid rearrangement is brought about by treatment of the dibromoolefin with BuLi under mild conditions. The success of these FBW reactions is quite solvent-dependent, and nonpolar hydrocarbon solvents (e.g., hexanes, toluene, benzene) work quite well, while use of ethereal solvents such as diethyl ether and tetrahydrofuran (THF) does not provide the desired polyyne product. This protocol was successfully applied to the formation of silyl, alkyl, alkenyl, and aryl polyynes, including di-, tri-, and tetrayne products, as well as the construction of two-dimensional carbon-rich molecules. A one-pot variant of this procedure is being developed and is particularly applicable toward the synthesis of polyyne natural products. Formation of a series of triisopropylsilyl end-capped polyynes, from the triyne to decayne, was achieved. Third-order nonlinear optical properties of these polyynes were evaluated. This study shows that the molecular second hyperpolarizabilities for the polyynes as a function of length increase at a rate that is higher than all other nonaromatic organic oligomers.