Premium
Total Synthesis of Lycoricidine and Narciclasine by Chemical Dearomatization of Bromobenzene
Author(s) -
Southgate Emma H.,
Holycross Daniel R.,
Sarlah David
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201709712
Subject(s) - bromobenzene , dihydroxylation , chemistry , hydroxylation , total synthesis , amide , stereochemistry , suzuki reaction , combinatorial chemistry , enantioselective synthesis , organic chemistry , palladium , catalysis , enzyme
The total synthesis of lycoricidine and narciclasine is enabled by an arenophile‐mediated dearomative dihydroxylation of bromobenzene. Subsequent transpositive Suzuki coupling and cycloreversion deliver a key biaryl dihydrodiol intermediate, which is rapidly converted into lycoricidine through site‐selective syn ‐1,4‐hydroxyamination and deprotection. The total synthesis of narciclasine is accomplished by the late‐stage, amide‐directed C−H hydroxylation of a lycoricidine intermediate. Moreover, the general applicability of this strategy to access dihydroxylated biphenyls is demonstrated with several examples.