Asymmetric synthesis of 3,3,5,5-tetrasubstituted 1,2-dioxolanes: total synthesis of epiplakinic acid F

Abstract

The first enantioselective total synthesis of epiplakinic acid F (1) was achieved through a pivotal step involving a radical-mediated asymmetric peroxidation of vinylcyclopropanes with molecular oxygen to construct highly substituted 1,2-dioxolanes. Subsequent conversions of the chiral 1,2-dioxolanes led to total synthesis of epiplakinic acid F (1) and the confirmation of its absolute configuration. The enantiomer of epiplakinic acid F methyl ester (2) was also prepared.

Marine natural products

“…), 633,634 bitungolide B (Theonella swinhoei), 635,636 plakortone L (Plakortis clathrata), 637,638 epiplakinic acid F (Plakinastrella sp. ), 639 and its methyl ester (Plakortis halichondrioides), 640,641 gracilioether F (Plakinastrella mamilaris), 642,643 taumycins A and B (revised 1033 and 1034, Fascaplysinopsis sp. ), 644,645 polydiscamides B-D (Ircinia sp.…”

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

“…A similar strategy based on the radical oxygenation of vinyl cyclopropanes was used for the synthesis of epiplakinic acid F ( 8 ) [ 65 ]. The vinyl cyclopropane 53 obtained from trans -1,2-cyclopropanedicarboxylate 52 , was then converted to 1,2-dioxolane 55 ( Scheme 7 ).…”

Advances in the synthesis of 1,2-dioxolanes and 1,2-dioxanes

“…16 However attention must be taken when using chiral lanthanum shifting agent, because epiplakinic acid F seemed to have been incorrectly assigned, as demonstrated by its total synthesis, where the optical sign matched with the opposite configuration. 22 Indeed optical rotation is strongly driven by the stereochemistry at C3 and C5 in this products family, cis and trans stereoisomers giving an opposite sign and the fatty chain exerting a lesser influence on it (Figure 2). Laurent Ferrié BioCIS Université Paris-Saclay The main difference between all plakinic acids relies on the side chain, which provides different chain lengths, unsaturations, and ramifications.…”