Studies on an Oxidative 1,4‐Addition to s‐trans‐1,3‐Dienes, a Key Reaction in a Strigol Total Synthesis

Abstract

Keywords: Oxidation / Olefination / Palladium / StereochemistryOxidation 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

Enzymatic Kinetic Resolution by Addition of Oxygen

“…[57] This important research highlights the ability of biotransformations to provide valuable enantioenriched intermediates on an industrially relevant scale.T hese compounds are key chiral intermediates in ap lethora of reported natural product syntheses (Scheme 11 b). Thus,t he enantiomerically enriched lactone 28 has been used to prepare the Corey lactone diol (leading to the synthesis of av ast selection of prostaglandins, [58] including the shown prostaglandin F2a [59] and latanoprost [60] ), jatrophane diterpenes such as PI-3, [61] the tigliane ring system, [62] callipeltoside A, [63] strigol, [64] methyl epijasmonate, [65] pseudomonic acid C, [66] carbonucleoside 29, [67] and various antivirals;the ketone 27 finds application in the synthesis of mupirocin H, [68] brefeldin A, [69] magellanine and magellaninone, [70] pseudomonic acid C, [71] 17-deoxyprovidencin, [72] and hybridalactone. [73] Scheme 8. a) CHMO Acineto -catalysed BV KR of five-and six-membered cyclic ketones (selected product examples shown);b )extension of the methodology to SmI 2 -mediated reductive cyclisation;c)complex natural products containing cycloheptanol and cyclooctanolc ore structures.…”