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The sclerophytin A adventure
Author(s) -
Paquette Leo A.
Publication year - 2001
Publication title -
the chemical record
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.61
H-Index - 78
eISSN - 1528-0691
pISSN - 1527-8999
DOI - 10.1002/tcr.1016
Subject(s) - dihydroxylation , triol , stereochemistry , adventure , chemistry , computer science , diol , organic chemistry , artificial intelligence , enantioselective synthesis , catalysis
The structural designation A originally made by Sharma and Alam to sclerophytin A was considered to be ambiguous and so notably strained relative to B that the latter was targeted for de novo synthesis (Scheme 1). Our two successful routes began with (5 S )‐( d ‐menthyloxy)‐2(5 H )‐furanone and involved the application of cycloaddition, Claisen ring expansion, transannular oxymercuration, and 1,2‐carbonyl transposition tactics to arrive at B . It was immediately apparent from polarity considerations and spectroscopic data that the antileukemic marine metabolite in question was in need of more deep‐seated structural revision. Following close re‐examination of an acquired authentic sample by advanced NMR techniques, the strong inference was made that sclerophytin A actually lacked a second oxygen bridge and was in reality the triol C . This conclusion was unequivocally confirmed by diverting an advanced intermediate generated earlier into a short sequence beginning with regiocontrolled dihydroxylation and terminating with configurational inversion at the secondary carbinol center. The status of other members of this series is also presented. © 2001 John Wiley & Sons, Inc. and The Japan Chemical Journal Forum Chem Rec 1:311–320, 2001.1