Oxidative Cyclization Reactions of Trienes and Dienynes: Total Synthesis of Membrarollin

Trienes and dienynes containing one electron-deficient double bond were shown to undergo regio- and stereoselective oxidative cyclization in the presence of permanganate ion to afford 2,5-bis-hydroxyalkyltetrahydrofurans (THF diols). The THF diols produced retained either alkene or alkyne functional...

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Bibliographic Details
Published in:	Journal of organic chemistry Vol. 74; no. 3; pp. 981 - 988
Main Authors:	Morris, Claire L, Hu, Yulai, Head, Geoff D, Brown, Lynda J, Whittingham, William G, Brown, Richard C. D
Format:	Journal Article
Language:	English
Published:	Washington, DC American Chemical Society 06-02-2009
Subjects:	Acetogenins - chemical synthesis Alkynes - chemistry Annonaceae - chemistry Chemistry Cyclization Exact sciences and technology Furans - chemical synthesis Furans - chemistry Heterocyclic compounds Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives Organic chemistry Oxidation-Reduction Polyenes - chemistry Preparations and properties Acetylenic compound Epimer Furan derivatives Selectivity Metal Stereochemistry Oxygen heterocycle Tetrahydrofurane Stereoselectivity Alkene Hydroxyl group Oxidation Acetogenin Chemical synthesis Protection Erythro stereoisomer Permanganates Diol Trienic compound Regioselectivity Dienic compound Ketone Total synthesis Enynic compound Polyketide Cyclization Absolute configuration Threo stereoisomer Ethylenic compound Alkyne
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Summary:	Trienes and dienynes containing one electron-deficient double bond were shown to undergo regio- and stereoselective oxidative cyclization in the presence of permanganate ion to afford 2,5-bis-hydroxyalkyltetrahydrofurans (THF diols). The THF diols produced retained either alkene or alkyne functionalities, which provided convenient handles for the metal oxo-mediated introduction of an adjacent THF ring with overall control of relative and absolute stereochemistry. Adjacent bis-THFs possessing threo-cis-threo-trans-erythro, threo-cis-threo-trans-threo, threo-cis-threo-cis-erythro, threo-cis-erythro-cis-threo, or threo-cis-erythro-trans-threo relationships were synthesized by appropriate selection of alkene geometry and methodology for the closure of the second ring. The threo-cis-threo-cis-erythro stereochemical arrangement is embodied within the bis-THF core units of a number of Annonaceous acetogenins including membrarollin, while trilobacin has a threo-cis-erythro-trans-threo configured core. As an application of the selective oxidative cyclization approach, a total synthesis of membrarollin was completed in 17 linear steps from dodecyne. The C21,C22 double epimer of membrarollin was also synthesized in 15 linear steps and without recourse to the use of hydroxyl group protection.
Bibliography:	ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23
ISSN:	0022-3263 1520-6904
DOI:	10.1021/jo802012a