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Studies on an Oxidative 1,4‐Addition to s ‐ trans ‐1,3‐Dienes, a Key Reaction in a Strigol Total Synthesis
Author(s) -
Galkina Anna,
Buff née Kranz Angelika,
Schulz née Samson Emmanuelle,
Hennig Lothar,
Findeisen Matthias,
Reinhard Gerd,
Oehme Ramona,
Welzel Peter
Publication year - 2003
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.200200671
Subject(s) - chemistry , total synthesis , diene , allylic rearrangement , wittig reaction , stereoselectivity , oxidative addition , medicinal chemistry , ring (chemistry) , stereochemistry , lithium (medication) , catalysis , organic chemistry , medicine , natural rubber , endocrinology
Abstract Oxidation of 4,6‐heptadienoic acid systems with hydrogen peroxide in the presence of a catalytic amount of diphenyl diselenide leads to 5‐(3‐hydroxypropenyl)dihydrofuran‐2‐one systems with defined relative configuration at the 4 and 7 positions (carboxylic acid numbering). A system having a six‐membered ring as part of the s ‐ trans ‐diene system was an intermediate in a strigol total synthesis; a second system lacking the six‐membered ring is the subject of the present publication. We accomplished a stereoselective synthesis of the diene system by (i) trapping a π‐allyl palladium complex with lithium diphenylphosphinite to give an allylic diphenylphosphane oxide and (ii) a subsequent Horner−Wittig reaction. The species that brings about the oxidative 1,4‐addition is benzeneperoxyseleninic acid. We also report observations that shed some light on the mechanism. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)