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Metathesis at an Implausible Site: A Formal Total Synthesis of Rhizoxin D
Author(s) -
Karier Pol,
Ungeheuer Felix,
Ahlers Andreas,
Anderl Felix,
Wille Christian,
Fürstner Alois
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201812096
Subject(s) - metathesis , history , chemistry , organic chemistry , polymerization , polymer
The new approach to the anticancer agent rhizoxin D described herein does not cohere with the conventional logic of metathesis, according to which macrocycles are best closed at a disubstituted olefinic site; rather, the trisubstituted C11−C12 alkene flanked by an allylic ‐OH group served as the pivot point for synthesis. This motif was attained in good yield and excellent selectivity by a sequence of alkyne metathesis, trans ‐hydrostannation and cross coupling. Because the exact same substructure is prominently featured in numerous other natural products, the underpinning strategy, though unusual, might bear more general relevance.