G. Yu. Ishmuratov

Transformations of peroxide products of olefins ozonolysis

The review summarizes the main laws of olefin ozonolysis and also further transformation of the peroxide products in “splitting” reactions and at the treatment with oxidants and reducers.

Synthesis of 9-Oxo- and 10-Hydroxy-2E-decenoic Acids

Experimental methods of synthesizing 9-oxo- and 10-hydroxy-2E-decenoic acids, biologically active compounds of the bee family (Apis mellifera L.), are reviewed.

Synthesis of 10-hydroxy- and 9-oxo-2E-decenoic acids from oleic acid

A practical synthesis of biologically active 10-hydroxy- and 9-oxo-2E-decenoic acids, components of mandibular gland secretion of honeybee (Apis mellifera L.), is developed using ozonolysis-reduction of oleic acid and 1,9-diacetoxynon-1-ene in the key steps.

SULFUR-CONTAINING DERIVATIVES OF MONO- AND BICYCLIC NATURAL MONOTERPENOIDS

Examples of thiylation of natural mono- and bicyclic and variously functionalized monoterpenoids (alkenes, ketones, epoxides, alcohols) and the latest transformation pathways of the newly formed sulfur-containing derivatives were reviewed.

Ozonolysis of alkenes and study of reactions of polyfunctional compounds: LXVIII. Investigation of transformations of peroxide products of olefins ozonolysis treated with hydroxylamine hydrochloride

Hydroxylamine hydrochloride efficiently reduces peroxide products of olefins ozonolysis into carbonyl compounds. Depending on the substrate character, solvent, and the treatment conditions the arising aldehydes transformed along the route aldehyde→aldoxime→nitrile→ester into individual compounds or their mixtures, or give the corresponding acetals.

Oxidation of Terpenoids with a Cyclohexanone Fragment by Performic Acid

Performic acid is a reactive, inexpensive, and available reagent for Baeyer–Villager oxidation of ketones that is used infrequently in the chemistry of cyclic terpene ketones, e.g., only for the oxidation of isocaranone [1] and allobetulone [2]. The goal of the present work was to expand the scope of this reagent for the oxidation of terpenoids with a cyclohexanone fragment. We found that Baeyer–Villager oxidation of 28-oxoallobetulin-3-one (1), carvomenthone (2), and menthone (3) by performic acid occurred regioand stereospecifically to give lactones 5–7, respectively. Oxidation of isomenthone (4) by H2O2–HCOOH caused racemization of the asymmetric center with the isopropyl substituent (probably due to keto–enol tautomerism under acidic conditions) to give a mixture of diastereomeric lactones 7 and 8 (1:1), in contrast with diastereospecific m-chloroperbenzoic acid [3].

Transformations of peroxide olefin ozonolysis products under the action of hydroxylamine and semicarbazide hydrochlorides in isopropyl alcohol

Hydroxylamine and semicarbazide hydrochlorides were shown to be efficient as reducing agents toward peroxide products of ozonolysis of various olefins with different degrees of substitution. The rate of the transformations aldehyde → aldehyde oxime → nitrile → ester upon treatment of peroxides with hydroxylamine hydrochloride in isopropyl alcohol was lower than in methanol.

Two approaches to the synthesis of 9-oxo-and 10-hydroxy-2E-decenoic acids, important components of queen substance and royal jelly of honeybees Apis mellifera

Two approaches to the synthesis of 9-oxo-and 10-hydroxy-2E-decenoic acids, biologically active components of queen substance and royal jelly of honeybees, respectively, were proposed starting with allyl bromide and 1,7-octadiene and using chemo-and regioselective transformations of the common intermediate building block 7-octen-1-ylacetate.

Synthesis of the Promising Chiral Synthon Isopropyl-4R-Methyl-6-Iodohexanoate from L-(-)-Menthol

A synthesis of the promising optically pure synthon isopropyl-4R-methyl-6-iodohexanoate based on ozonolytic transformation of the product of regiospecific dehydratation of L-(-)-menthol, (R)-p-menth-3-ene, into 2,6R-dimethyl-8-hydroxyoctan-3-one was proposed.

Ozonolytic Decyclization of (R)-4-Menthen-3-one

Ozonolytic decyclization of (R)-4-menthen-3-one is accompanied by fragmentation of the isobutyl group, leading to ω-functionalized 3-methylpentanoic acid derivatives.