Kinetics of enzymatic synthesis of geranyl butyrate by transesterification in various supercritical fluids

The transesterification of methyl butyrate, ethyl butyrate and butyl butyrate to geranyl butyrate was investigated in supercritical carbon dioxide. The effect of chain length of the butyrate on the rate of transesterification was investigated. The initial rates followed the trend: ethyl butyrate < butyl butyrate < methyl butyrate. The transesterification of butyl butyrate to geranyl butyrate in various supercritical fluids such as ethylene, methane, ethane was also examined. The initial rate of transesterification of butyl butyrate in different supercritical fluids followed the order: ScCO2 < ScC2H6 < ScC2H4 < ScCH4. The highest initial rate was obtained in supercritical methane and the reasons for this observation were proposed. The Ping-Pong Bi-Bi model with inhibition by both acid and alcohol was used to model the experimental data and determine the kinetics of the reaction. (C) 2010 Elsevier B.V. All rights reserved.

An expeditious enantiospecific total synthesis of (+)-7-epi-goniofufurone

Stereoselective synthesis of styryl lactone, (+)-7-epi-goniofufurone was achieved in high yield via simple transformations from tartaric acid. The key step involves the successive stereoselective reduction of ketones with borohydride and selectride.

Approaches to sesquiterpenes containing three contiguous quaternary carbon atoms. Synthesis of 3-methoxythapsene

Synthetic approach to 3-alkoxythapsane, comprising of the carbon framework of a small group of sesquiterpenes containing three contiguous quaternary carbon atoms has been described. A combination of alkylation, orthoester Claisen rearrangement and intramolecular diazoketone cyclopropanation has been employed for the creation of the three requisite contiguous quaternary carbon atoms.

Facile enantiospecific synthesis of (+)-iso-cladospolide B

Enantiospecific synthesis of bio-active butenolide (+)-iso-cladospolide B from D-(-)-tartaric acid in a short synthetic sequence is presented. Pivotal reaction sequence includes cross metathesis of an alkene and Wittig olefination. (C) 2010 Elsevier Ltd. All rights reserved.

A total synthesis of the epoxyquinone based antifungal natural product (±)-ambuic acid

A total synthesis of the recently isolated polyketide natural product (+/-)-ambuic acid has been accomplished from the readily available Diels-Alder adduct of cyclopentadiene and 2-allyl-p-benzoquinone through a simple sequence with sound stereocontrol. (c) 2005 Elsevier Ltd. All rights reserved.

Observation of a chiral smectic phase in azobenzene-linked bolaamphiphiles containing free sugars

Amphiphilic sugars exhibit both lyotropic and thermotropic liquid-crystalline behavior. Interestingly, in spite of the abundance of chiral centers in amphiphilic sugars, their liquid-crystalline phases do not exhibit macroscopic chirality. Herein, we report on the first observation of macroscopic chirality in sugar-based bolaamphiphiles containing free hydroxyl groups. The manifestation of the chiral smectic C* phase in these bolaamphiphiles has been observed to be critically dependent on the presence of the azobenzene moiety and the suitable length of the methylene spacer. These results imply that by suitable selection of linker groups, mesogenic bolaamphiphiles possessing macroscopic chirality can be designed using a variety of naturally available sugar derivatives.

Synthesis of neoglycopeptides and analyses of their biodistributionin vivo to identify tissue specific uptake and novel putative membrane lectins

Complex typeN-linked oligosaccharides derived from fetuin, fibrinogen and thyroglobulin were coupled to acetyltyrosine affording a series of neoglycopeptides with retention of terminal structures and the beta-anomeric configuration of their reducing endN-acetylglycosamine residue. The neoglycopeptides thus synthesized could be labelled to high specific activities with125I in the aromatic side chain of tyrosine. Analysis of the fate of these neoglycopeptides in conjunction with inhibition with asialofetuin and oligosaccharides of defined structure in micein vivo revealed the uptake of galactosylated biantennary compound by kidneys, in addition to the known itinerary of triantennary galactosylated complex oligosaccharide from fetuin to liver and the galactosylated biantennary chain with fucosylation in the core to bone marrows. On the other hand, the agalacto, aglucosamino biantennary chains with and without fucosylation in the core region are taken up by submaxillary glands while the conserved trimannosyl core with fucose is primarily concentrated in stomach tissue. These studies thus define new routes for the uptake of complexN-linked glycans and also subserve to identify lectins presumably involved in their recognition.

Synthetic application of the diels-alder adduct of β-trans-ocimene and maleic anhydride-II. An approach towards the synthesis of valerenic acid

By a series of reactions the Diels-Alder adduct IV of maleic anhydride and β-trans-Ocimene gave 1-hydroxy-1,4-dimethyl-7-hydroxymethyloctahydroindane (XII). Its further synthetic elaboration furnished 1,4-dimethyl-7-(2-ethoxycarbonyl-1-propenyl)-Δ1-octahydroindane of the valerenic acid skeleton.

Studies in sesquiterpenes—XXIV *1: Synthesis of (±)-cadinene dihydrochloride

A total synthesis of (±)-4-isopropyl-trans-decalin-1,6-dione, a key intermediate in the cadinane series, and its conversion into (±)-cadinene dihydrochloride, is reported.

Studies in oxasteroids—I : Synthesis of 3-cyano-3-methyl-7-methoxychroman-4-one and the structure of an “abnormal” product

A synthesis of 3-cyano-3-methyl-7-methoxychroman-4-one is reported. The structure of an “abnormal” product obtained during isomerization (III) with potassium t-butoxide in t-butanol, followed by alkylation with methyl iodide has been proved to be 3-t-butoxy-2-cyano- 2-mehthyl-2′,4′-dimethoxypropiophenone (IVa).

Studies in sesquiterpenes—XXV : A synthesis of α-selinene

The conversion of α-cyperone into α-selinene is described.

Studies in sesquiterpenes—XXVI : Synthesis of 2,2,6-trimethyl-3-oxo-1-carbomethoxybicyclo[0,3,3]octane, a degradation product of patchouli alcohol

The synthesis of the title compound is described and results of some experiments on the degradation of patchouli alcohol are reported.

Synthetic investigations on testerone and its analogues—I *1: The total synthesis of 8-isotestosterone and its anthracene analogue

The total synthesis of 8-isotestosterone (II) and the corresponding anthracene analogue (III) following the benzohydrindane route is reported. Catalytic hydrogenation of trans-1β-acetoxy-8-methyl-4,5-(3′-methyl-4′-hydroxybenzo)-hydrindane (V) followed by oxidation has furnished two isomeric tricyclic keto acetates, viz. 1β,2α-(3′-acetoxycyclopentano)-2,5-dimethyl-6-keto-1α,2,3,4,4aα,-5α,6,7,8,8aα-decahydronaphthalene (VII) and 1β,2α-(3′-acetoxycyclopentano)-2,5-dimethyl-6-keto-1α,2,3,4,4aβ,5,6,7,8,8aβ-decahydronaphthalene (IX) which are cis-non-steroid and cis-steroid configurations of the same cyclopentano-cis-decalins. A difference in the direction of enolization of the keto acetate (VII) in alkylation reaction and enol acetylation towards the methine and the methylene carbon atoms respectively has been observed.