Redox electron-transfer reactions: electrochemically mediated rearrangement, mechanism, and a total synthesis of daucene.
The term "housane" refers to molecules possessing a bicyclo[2.1.0]pentane core. One was designed, synthesized, and used as a precursor of daucene, a member of the carotane class of sesquiterpenes. The total synthesis was completed, thereby marking the first time that housane-derived cation radicals have been used as the key intermediate in the synthesis of a natural product. The transformation used in the construction and featured in the text involves an oxidation to generate the cation radical via either a chemically or an electrochemically mediated electron transfer, the latter process using tris(p-bromophenyl)amine as the mediator. The two methods are compared, and guiding principles are formulated to assist in deciding how best to implement each. Both processes afford an unfavorable equilibrium state that is subsequently drained toward the product by two irreversible events, viz., a 1,2 carbon migration to the site that best stabilizes a positive charge and a second electron transfer, this time being a highly exothermic reduction of the rearranged species to generate the neutral product. A mechanistic proposal calling for the use of a catalytic quantity of the electrochemical mediator and the consumption of exceptionally small quantities of current is advanced. Experimental deviations from these predictions are noted, and a rationale to account for them is presented. Finally, significant differences were noted between the cyclic voltammograms of housanes bearing a CH2OR substituent rather than a methyl group at the bridgehead carbon. Those having the inductively withdrawing group displayed broad and ill-defined curves. The differences were investigated quantum mechanically, and a stereoelectronic argument is formulated stating that broadness of the curve for the ROCH2-substituted systems is the result of a time-averaged sampling of the HOMO energies over the distribution of conformers. The possible generality of the stereoelectronic effect is noted.
Park
Young Sam
YS
Department of Chemistry & Biochemistry, University of California, Santa Barbara, California 93106, USA.
Little
R Daniel
RD
D000588:Amines / Q000737:chemistry; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis*; D002384:Catalysis; D003517:Cyclopentanes / Q000737:chemistry; D004563:Electrochemistry; D004579:Electron Transport; D005609:Free Radicals / Q000737:chemistry; D007094:Imides / Q000737:chemistry; D008956:Models, Chemical; D010084:Oxidation-Reduction; D012717:Sesquiterpenes / Q000138:chemical synthesis*; D013816:Thermodynamics
D000588:Amines; D001643:Bridged Bicyclo Compounds; D003517:Cyclopentanes; D005609:Free Radicals; D007094:Imides; D012717:Sesquiterpenes; C533056:daucene; C038867:diazene