Open AccessSynthesis of Vitisins A and D Enabled by a Persistent Radical Equilibrium
Author(s) -
Kevin Romero,
Mitchell H. Keylor,
Markus Grießer,
Xu Zhu,
Ethan Strobel,
Derek A. Pratt,
Corey R. J. Stephenson
Publication year - 2020
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.0c01714
Subject(s) - chemistry , isomerization , molecule , dimer , computational chemistry , radical , combinatorial chemistry , organic chemistry , catalysis
The first total synthesis of the resveratrol tetramers vitisin A and vitisin D is reported. Electrochemical generation and selective dimerization of persistent radicals is followed by thermal isomerization of the symmetric C8b-C8c dimer to the C3c-C8b isomer, providing rapid entry into the vitisin core. Computational results suggest that this synthetic approach mimics Nature's strategy for constructing these complex molecules. Sequential acid-mediated rearrangements consistent with the proposed biogenesis of these compounds afford vitisin A and vitisin D. The rapid synthesis of these complex molecules will enable further study of their pharmacological potential.