[4 + 4]-cycloaddition of isoprene for the production of high-performance bio-based jet fuel

Abstract

Isoprene was efficiently converted to 1,6-dimethyl-1,5-cyclooctadiene (DMCOD) by selective [4 + 4]-cycloaddition with a catalyst formed by in situ reduction of [(MePI)FeCl(μ-Cl)]2 (MePI = [2-(2,6-(CH3)2-C6H3-N[double bond, length as m-dash]C(CH3))-C4H5N]). DMCOD was isolated in 92% yield, at the preparative scale, with a catalyst loading of 0.025 mol%, and a TON of 3680. Catalytic hydrogenation of DMCOD yielded 1,4-dimethylcyclooctane (DMCO). The cyclic structure and ring strain of DMCO afforded gravimetric and volumetric net heats of combustion 2.4 and 9.2% higher, respectively, than conventional jet fuel. In addition, the presence of methyl branches at two sites resulted in a −20 °C kinematic viscosity of 4.17 mm2 s−1, 48% lower than the maximum allowed value for conventional jet fuel. The ability to derive isoprene and related alcohols readily from abundant biomass sources, coupled with the highly efficient [Fe]-catalyzed [4 + 4]-cycloaddition described herein, suggests that this process holds great promise for the economical production of high-performance, bio-based jet fuel blendstocks.