Gold-catalyzed generation of vinylthionium ions and the development of an organocatalytic, asymmetric (4+3)-cycloaddition reaction

Abstract

[ACCESS RESTRICTED TO THE UNIVERSITY OF MISSOURI AT REQUEST OF AUTHOR.] An allylic benzoate ester was prepared and used as a progenitor of vinylthionium ions for (4+3)-cycloaddition reactions. The chemistry was limited to 2-substituted and 2,5-disubstituted furans. In the case of 2-substituted furans, only Friedel-Crafts alkylation products were procured. In the case of 2,5-disubstituted furans, (4+3)-cycloaddition products were furnished in good yield. A catalytic, asymmetric variant using 2,5-dialkylfurans and chiral acids to procure cycloaddition products was unsuccessful. There was an opportunity to overcome the Friedel-Crafts alkylation problem that arose in a gold-catalyzed cycloaddition project. A sulfur-substituted unsaturated ester and alcohol were prepared, but silyl migration was a considerable problem upon activation by various agents. The problem of silyl migration was circumvented, but the target aldehyde was unreactive toward dienes in the presence of various Lewis acids. In further pursuit of an asymmetric (4+3)-cycloaddition reaction, 2-substituted furans were reacted with 2-tosyloxycyclopentanone in the presence of K2HPO4/H2O in perfluorobenzene as solvent and 30 mol% of an amino alcohol catalyst developed by David MacMillan. Enantioselectivities were modest for 2-alkylfurans and excellent for 2-arylchalcogenofurans (90% ee). 3-Substituted furans also work in this process.