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Strategies for the Total Asymmetric Synthesis of Heliannuols K and L: Scope and Limitations
Author(s) -
Lecornué Frédéric,
Paugam Renée,
Ollivier Jean
Publication year - 2005
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200400908
Subject(s) - chemistry , enantioselective synthesis , total synthesis , intramolecular force , scope (computer science) , combinatorial chemistry , formal synthesis , stereochemistry , organic chemistry , catalysis , computer science , programming language
Abstract Kulinkovich reactions of oxa‐esters bearing terminal double bonds afford cyclopropanols by intramolecular cyclization. These can undergo Saegusa oxidation to provide β‐chloro‐oxacycloalkanones and can then be then dehydrohalogenated into oxacycloalkenones. Through a judicious choice of starting esters, diverse aryl‐fused benzoxocinones possessing the basic skeleton of sesquiterpenes, such as heliannuols, can be obtained. Although the syntheses of certain compounds in racemic form seem accessible, however, improvements through new strategies are still required for the total asymmetric synthesis. This article describes the first synthesis of enantiomerically enriched OMe‐heliannuol K and the first stereo‐ and enantioselective synthesis of heliannuol L, and new approaches and studies of their limitations in the preparation of these products are detailed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)