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Enantioselective Total Syntheses of Cyathane Diterpenoids
Author(s) -
Nakada Masahisa
Publication year - 2014
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.201402019
Subject(s) - total synthesis , enantioselective synthesis , intramolecular force , aldol reaction , chemistry , stereochemistry , cyclopropanation , stereoselectivity , catalysis , organic chemistry
A Personal Account describing the enantioselective total syntheses of cyathane diterpenoids achieved in the Nakada group. A convergent approach to the cyathane scaffold, the [5‐6‐7] tricyclic carbon skeleton commonly found in cyathane diterpenoids, has been developed using the catalytic asymmetric intramolecular cyclopropanation ( CAIMCP ) and baker's yeast reduction. This approach has been successfully applied for the enantioselective total syntheses of (+)‐allocyathin B 2 , (−)‐erinacine B , and (−)‐erinacine E . The total synthesis of (−)‐erinacine E has been achieved via the acyl group migratory intramolecular aldol reaction, which prevents the retro‐aldol reaction and allows the construction of the strained structure. The highly efficient and stereoselective total syntheses of (−)‐scabronines G , A , D , and (−)‐episcabronine A have been achieved via the oxidative dearomatization/inverse electron demand Diels – Alder reaction cascade. Cascade reactions comprising three and five consecutive reactions were employed for the highly efficient total syntheses of (−)‐scabronine A and (−)‐episcabronine A , respectively.