Synthesis and stereochemistry of some bicyclic gamma-lactones from parasitic wasps (Hymenoptera: Braconidae). Utility of hydrolytic kinetic resolution of epoxides and palladium(II)-catalyzed hydroxycyclization-carbonylation-lactonization of ene-diols.

A palladium(II)-catalyzed hydroxycyclization-carbonylation-lactonization sequence with appropriate pent-4-ene-1,3-diols provides efficient access to the bicyclic gamma-lactones, 5-n-butyl- and 5-n-hexyltetrahydrofuro-[3,2-b]furan-2(3H)-ones (3) and (4), respectively, in both racemic and enantiomeric forms. Some of the substrate pent-4-ene-1,3-diols of high enantiomeric excess (ee) have been derived from racemic terminal epoxides by hydrolytic kinetic resolution (HKR) using cobalt (III)-salen complexes. (9Z,12R)-(+)-Ricinoleic acid also serves as a "chiral pool" source of other pent-4-ene-1,3-diols. These syntheses and enantioselective gas chromatography confirm the structures and absolute stereochemistry of the lactones in some species of parasitic wasps (Hymenoptera: Braconidae). The highly abundant 5-n-hexyltetrahydrofuro-[3,2-b]furan-2(3H)-one (4) in Diachasmimorpha kraussii and D. longicaudata is of high ee (>99%) with (3aR,5R,6aR) stereochemistry.

Carbon hydroxylation of alkyltetrahydropyranols: a paradigm for spiroacetal biosynthesis in Bactrocera sp.

[figure: see text] In a number of Bactrocera species the penultimate step in the biosynthesis of spiroacetals is shown to be the hydroxylation of an alkyltetrahydropyranol followed by cyclization. The monooxygenases that catalyze this side chain hydroxylation show a strong preference for oxidation four carbons from the hemiketal center, to produce the spiroacetal. The hydroxy spiroacetals observed in Bactrocera appear to derive from direct oxidation of the parent spiroacetals and not from alternate precursors.

Synthetic studies of the HIV-1 protease inhibitive didemnaketals: stereocontrolled synthetic approach to the key mother spiroketals.

The stereocontrolled synthesis of (2S,4R,6R,8S,10S,1'R,1' 'R)-2(acetylhydroxymethyl)-4,10-dimethyl-8(isopropenylhydroxymethyl)-1,7-dioxaspiro[5,5]undecane (4a) and its C1' '-epimer (4b), the key mother spiroketals of the HIV-1 protease inhibitive didemnaketals from the ascidian Didemnum sp., has been carried out through multisteps from the natural (R)-(+)-pulegone, which involved the diastereoselective construction of four chiral carbon centers(C-2, C-6, C-8, and C-1') by intramolecular chiral induce.

Chemistry of fruit flies: Glandular secretion ofBactrocera (Polistomimetes) visenda (Hardy).

The major component (>90% of volatiles) of the male rectal glandular extract of the nonpest speciesBactrocera visenda (Hardy) is 3-methyl2-butenyl acetate, with minor components being the isomeric 3-methyl-3-butenyl acetate, the homologous esters, 3-methyl-2-butenyl propanoate and 3-methyl-2-butenyl formate, along with 3-methyl-2-buten-1-ol, 3-methyl-2-butenal, and 3-methylbutyl acetate. None of these compounds has been identified previously from aBactrocera species, supporting the view thatBactrocera visenda is taxonomically distant from otherBactrocera species identified from the Australian mainland. This collection of compounds adds to the known types utilized by dipteran species and emphasizes their extensive biosynthetic capability.

Chemistry of fruit flies: Nature of glandular secretion and volatile emission ofBactrocera (bactrocera) cacuminatus (Héring).

The major component of the rectal glandular extract and volatile emission of maleBactrocera cacuminatus is racemic 1,7-dioxaspiro[5.5]undecane. l-Hydroxy-5-nonanone as its open chain form, together with 6-n-butyl-3,4-dihydro-2H-pyran are minor components. 1,7-Dioxaspiro[5.5]undecan-4-ol is present at a low level and is shown to be exclusively the diastereomer with an equatorial hydroxy group by comparison with synthesized samples of both epimers. Examination of the trifiuoroacetate by chiral gas chromatography has established the (4S,6S) stereochemistry (ca. 80% ee). The presence of 1,7-dioxaspiro[5.5]undecan-3-ol, or its isomerization product, 1,6-dioxaspiro[4.5]decan-2-ylmethanol, could not be confirmed. Trapping of the volatiles released by sexually mature male flies at dusk revealed that a number of the glandular components described above are released at mating time. Reexamination of the glandular secretion of sexually mature female olive flies (B. oleae) has failed to confirm the presence of any 1,7-dioxaspiro[5.5]undecanols, with the only volatile component (other than fatty acids) being 1,7-dioxaspiro[5.5]undecane.

Chemical studies of rectal gland secretions of some species ofBactrocera dorsalis complex of fruit flies (diptera: Tephritidae).

Male-produced rectal gland secretions of a number of species now considered to be members of theBactrocera dorsalis complex of fruit flies have been examined by combined gas chromatography-mass spectrometry. The structures of a number of previously unreported compounds have been confirmed by synthesis and Chromatographic comparisons. Compounds identified in these secretions include fatty acids, esters, amides, keto alcohols, diols and spiroacetals. These chemical findings are in agreement with taxonomic revisions based on other criteria.