Total Syntheses of Basiliolide A₁, Basiliolide A₂, Basiliolide C, and their Structural Analogues

Abstract

A small focussed library of basiliolides including basiliolide A1, basiliolide A2, basiliolide C, and their structural analogues have been prepared for structure–activity‐relationship studies. The synthesis features a cyclopropanation/ring‐opening strategy to establish the C‐8 stereogenic centre by using the cyclopropanation substrate with the appropriate alkene geometry; an IMDA (intramolecular Diels–Alder) reaction to construct the seco acid derivatives; and a biomimetic O‐acylation to form the unprecedented seven‐membered acyl ketene acetal ring. The des‐D‐ring analogues were prepared by an IMDA/decarboxylation strategy. Moreover, an asymmetric catalytic cyclopropanation reaction has been developed; this provided an optically enriched intermediate for asymmetric synthesis.

Sarco/Endoplasmic Reticulum Calcium ATPase Inhibitors: Beyond Anticancer Perspective

“…A considerable effort has also been invested into the organic synthesis of basiliolides as well as transtaganolides. 108−111 Successful syntheses of basiliolide B (16, Figure 7), 112,113 transtaganolides A, B, C, and D, 114 compound 15, basiliolides A2 and C 115 were reported, suggesting that obtaining transtaganolides and basiliolides for further biological studies does not need to rely on plant isolates from seasonal plants.…”

“…Further biological activity of basiliolides also includes the activation of the nuclear factor of activated T cells (NFAT), nuclear factor κ-light-chain-enhancer of activated B cells (NF-κB), and activator protein 1 (AP-1). A considerable effort has also been invested into the organic synthesis of basiliolides as well as transtaganolides. − Successful syntheses of basiliolide B ( 16 , Figure ), , transtaganolides A, B, C, and D, compound 15 , basiliolides A2 and C were reported, suggesting that obtaining transtaganolides and basiliolides for further biological studies does not need to rely on plant isolates from seasonal plants.…”

Furan Oxidation Reactions in the Total Synthesis of Natural Products

“…The Tf 2 O-induced cyclization of these compounds afforded (±)basiliolides A 1 (372) and A 2 (373) (Scheme 90). 139 Alternatively, pyranone 368 was converted into (±)basiliolide C (374) (Scheme 91). Some structural analogues of basiliolides A-C were also synthesized.…”

“…Some structural analogues of basiliolides A-C were also synthesized. 139 This oxidative system was also applied for the synthesis of a potential antitumor agent, FR901464 (378), isolated from the fermentation broth of Pseudomonas sp. No.…”