General Methodologies Toward cis-Fused Quinone Sesquiterpenoids. Enantiospecific Synthesis of the epi-Ilimaquinone Core Featuring Sc-Catalyzed Ring Expansion

General Methodologies Toward cis-Fused Quinone Sesquiterpenoids. Enantiospecific Synthesis of the epi-Ilimaquinone Core Featuring Sc-Catalyzed Ring Expansion

A stereocontrolled approach to the cis-decalin framework of clerodane diterpenes and biologically active quinone sesquiterpenes is reported. Starting from an inexpensive optically pure tetrahydroindanone, Birch reductive alkylation builds two new contiguous chiral centers—one of which is quaternary...

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Bibliographic Details
Main Authors: Hilan Z. Kaplan, Victor L. Rendina, Jason S. Kingsbury
Format: Article
Language:English
Published: MDPI AG 2017-06-01
Series:Molecules
Subjects:
quinone natural products
quaternary carbon synthesis
cis-decalin
scandium triflate
catalytic ring expansion
homologation
(trimethylsilyl)diazomethane
hexahydroindanones
5-epi-ilimaquinone
5-epi-isospongiaquinone
Online Access:http://www.mdpi.com/1420-3049/22/7/1041
Description
Summary:A stereocontrolled approach to the cis-decalin framework of clerodane diterpenes and biologically active quinone sesquiterpenes is reported. Starting from an inexpensive optically pure tetrahydroindanone, Birch reductive alkylation builds two new contiguous chiral centers—one of which is quaternary and all-carbon-substituted. Also featured is a highly regioselective diazoalkane—carbonyl homologation reaction to prepare the 6,6-bicyclic skeleton. Therein, the utility of Sc(OTf)3 as a mild catalyst for formal 1C insertion in complex settings is demonstrated.
ISSN:1420-3049

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