Bruce P. Branchaud, Bart J. Dahl, and Ying Lin. University of Oregon, Eugene, OR
Several biaryl lactones have been synthesized and are capable of energy-driven directed bond rotation about the aryl-aryl bond axis. These systems can be considered to be prototypical synthetic molecular motors. One class of triortho-substituted biaryl lactones are achiral and use chiral nucleophilic "fuels" to break a lactone ring diastereoselectively to afford non-racemizing atropisomeric biaryls resulting in a 90 degree directed bond rotation. Subsequent re-lactonization using an acyl-activating "fuel" exploits the orthogonal reactivity of the two reactive ortho substituents on the upper ring, resulting in 180 degree directed bond rotation. This process can be repeated, resulting in iterative net unidirectional bond rotation. Another class of triortho-substituted biaryl lactones are chiral and use achiral nucleophilic "fuels" in directed bond rotation following a mechanism similar to that previously stated. A primary advantage of these systems is that, in principle, only 2 synthetic steps are required to achieve 180 degree directed bond rotation in high yields. Another advantage is that numerous nucleophilic "fuels" are capable of driving the lactone ring-opening and numerous methods of acyl activation (e.g. acid, oxidation, photochemical, electrochemical) are capable of driving the re-lactonization. The synthesis, development, and characterization of each prototypical synthetic biaryl molecular motor will be presented.
Back to Molecular Devices and Motors (Invited Speakers Only)
Back to The 61st Northwest Regional Meeting (June 25 - 28, 2006)