Towards the Total Synthesis of Mycaperoxide B: Probing Biosynthetic Rationale

Abstract

Studies towards the biomimetic synthesis of mycaperoxide B (1) are described. We have established the synthesis of four diastereoisomers of mycaperoxide B methyl ester (1a) by employing a Michael addition across an α,β-unsaturated ester precursor 2 as the key step. This result strongly suggests stereocontrol in the addition of the hydroperoxide function-

Cobalt-Catalyzed Oxygenation/Dearomatization of Furans

“…In general, α-peroxy carbonyl compounds can be difficult to synthesize and isolate in high yield. 30–32 The products were found to be sensitive to chromatography, which was determined by converting the silyl peroxide to the more stable silyl ether ( 10 , Scheme 7) using triphenylphosphine, 33 which resulted in an increased yield compared to the silyl peroxide (Table 2, entry 1). The products were also found to decompose during the course of the reaction.…”

Peroxides with Anthelmintic, Antiprotozoal, Fungicidal and Antiviral Bioactivity: Properties, Synthesis and Reactions

“…Diastereomeric cyclic peroxides 171 , one of which is the methyl ester of the mycaperoxide B ( 116 ), were prepared from protected hydroxyperoxide 167 ( Scheme 25 ) [ 106 ]. In the first step, peroxide 167 was oxidized to aldehyde 168 , which was converted into unsaturated ester 169 by Wittig reaction.…”

Relative and Absolute Stereochemistry of Diacarperoxides: Antimalarial Norditerpene Endoperoxides from Marine Sponge Diacarnus megaspinorhabdosa

“…These availabilities have been demonstrated synthetically [30,31]. The diacarperoxide class provides us potent compounds acting against malaria.…”