3-(4-Methyl-3-pentenyl)-2(5H)-furanone, α,α-Acariolide and 4-(4-Methyl-3-pentenyl)-2(5H)-furanone, α,β-Acariolide:

Abstract

A new monoterpene lactone from the acarid mite, Schwiebea araujoae, was elucidated without its isolation by GC/FT-IR and GC/MS analyses to be 3-(4-methyl-3-pentenyl)-2(5H)-furanone (1) and tentatively named as alpha,alpha-acariolide. The structure of 1 was identified by its synthesis from alpha-bromo-gamma-butyrolactone via 4 reaction steps. The synthesized compound gave the same GC/MS and GC/FT-IR spectra as those of the natural product. The other monoterpene lactone was likewise elucidated from the unidentified Rhizoglyphus mite to be 4-(4-methyl-3-pentenyl)-2(5H)-furanone (2) and named as alpha,beta-acariolide; it was also identified by its synthesis in 5 reaction steps from the same butyrolactone as the starting material. GC/MS and GC/FT-IR spectra of the preparation were identical to those of the natural product.

(E)-2-(2-Hydroxyethylidene)-6-methyl-5-heptenal (α-Acariolal) and (E)-2-(2-Hydroxyethyl)-6-methyl-2,5-heptadienal (β-Acariolal), Two New Types of Isomeric Monoterpenes…

“…After evaporating the solvent, the residual oil was puriˆed in a silica gel column, eluting with hexane-ether (1:1) to give 8 (120 mg, 93z). Methyl 2-[2-(tert-butyldimethylsilyl)oxyethyl]-6-methyl-2-methylsulˆnyl-5-heptenoate (9). Protected methylthio compound 8 (120 mg, 0.33 mmol) dissolved in methanol (5 ml) was oxidized by sodium metaperiodate (75 mg, 0.35 mmol) dissolved in a minimum volume of water at 09 C, and the reaction mixture was stirred at r.t. for 14 h. The mixture was then diluted with ether, washed with brine, and dried over Na2SO4.…”

“…3. a-(4-Methyl-3-pentenyl)-a-methylthio-g-butyrolactone (5) prepared by the reported method 9) was hydrolyzed by KOH to give 2-(2-hydroxyethyl)-6-methyl-2-methylthio-5-heptenoic acid (6). After protecting the carboxyl group of 6 by (trimethylsilyl)diazomethane and the hydroxy group by tert-butyldimethylchlorosilane, resulting methyl 2-[2-(tert-butyldimethylsilyl)oxy- ethyl]-6-methyl-2-methylthio-5-heptenoate (8) was oxidized with sodium metaperiodate.…”

A Unified Strategy for the Regiospecific Assembly of Homoallyl-Substituted Butenolides and γ-Hydroxybutenolides: First Synthesis of Luffariellolide

“…Figure 2 To probe the feasibility of this strategy, especially the crucial sp 3 -sp 3 cross-coupling of the hitherto unknown Grignard reagent 6 with an allylic partner, 12 we initially chose as targets the structurally simple natural products a,b-acariolide (11) 13 and its g-hydroxyl derivative 14 12 (Scheme 2). The precursor of 6, 4-(chloromethyl)-2-(triisopropylsilyloxy)furan (8), 15 was prepared from the readily available butenolide 7 16 as previously described.…”

The use of the lactone motif in chemical communication

“…The oxidized monoterpenes a,a-acariolide (141) and a,bacariolide (142) were identied from the acarid mites, Schwiebea araujoae and Rhizoglyphus sp., respectively. 157 Both lactones have been synthesized from bromocyclopentanone. 157 Lactone 142 is also available using a silyloxyfuran strategy.…”

“…157 Both lactones have been synthesized from bromocyclopentanone. 157 Lactone 142 is also available using a silyloxyfuran strategy. 158 The related lactone b-acariolide ( 143) is an oil gland secretion product of the mold mite, Tyrophagus putrescentiae.…”