Asymmetric synthesis of griffipavixanthone employing a chiral phosphoric acid-catalyzed cycloaddition
Files
Accepted manuscript
Supporting documentation
Date
2019-01-09
Authors
Smith, Michael J.
Reichl, Kyle D.
Escobar, Randolph A.
Heavey, Thomas J.
Coker, David F.
Schaus, Scott E.
Porco, John A.
Version
Accepted manuscript
OA Version
Citation
Michael J Smith, Kyle D Reichl, Randolph A Escobar, Thomas J Heavey, David F Coker, Scott E Schaus, John A Porco. 2019. "Asymmetric Synthesis of Griffipavixanthone Employing a Chiral Phosphoric Acid-Catalyzed Cycloaddition." JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Volume 141, Issue 1, pp. 148 - 153 (6). https://doi.org/10.1021/jacs.8b12520
Abstract
Asymmetric synthesis of the biologically active xanthone dimer griffipavixanthone is reported along with its absolute stereochemistry determination. Synthesis of the natural product is accomplished via dimerization of a p-quinone methide using a chiral phosphoric acid catalyst to afford a protected precursor in excellent diastereo- and enantioselectivity. Mechanistic studies, including an unbiased computational investigation of chiral ion-pairs using parallel tempering, were performed in order to probe the mode of asymmetric induction.