This review presents methods for functionalisation of macroheterocycles occurring both with preservation and alteration of their core. It is shown that the most common methods do not affect the main ring. While functionalisation of macroheterocycles accompanied by both a decrease and an increase of their size is less common, the examples given in the literature indicate the prospects of macroheterocycle functionalisation by described methods in direct synthesis of substances for different purposes: pharmacologically active compounds, selective ligands for various ( mainly transient and rare-earth) metals, odorants, etc.

The condensation of 7-oxooctyl 7-oxooctanoate and bis(7-oxooctyl) hexanedioate with bicyclo-[2.2.1]heptane-2- endo ,3- endo -dicarbohydrazide and its 5- endo ,6- endo - and 5- endo ,6- exo -dihydroxy derivatives obtained from dimethyl norbornene-2- endo ,3- endo -dicarboxylate gave the corresponding macrocyclic lactones containing a ketone azine fragment instead of the expected hydrazide moiety.

An optically pure macrolide containing 1,3-dioxolane, gem-dimethylcyclopropyl, and hydrazide fragments was synthesized from (+)-3-carene via [1+1]-condensation of the product from sequential ozonolysis—reduction and Tishchenko disproportionation of (3S,4S)-[(3R,4R)-4-isopropyl-3-methyl-6-oxoheptyl]-4-isopropyl-3-methyl-6-oxoheptanoate with the hydrazide of L-(+)-tartaric acid acetonide.

The synthesis of two potentially useful optically active 23- and 30-membered macrolides containing a 1,2-diol system and dihydrazide fragments was developed starting from tetrahydropyran. It was based on [1+1]-condensation of 7-oxooctyl-7-oxooctanoate and bis(7-oxooctyl)hexanedioate with L-(+)-tartaric acid hydrazide.

New capabilities for the synthetic use of (R)-4-menthen-3-one were demonstrated using as examples (3S)-methylundec- and (2S)-methyldec-1-ylbromides, key synthons for (S,S,S)-diprionylacetate (sex pheromone of pine sawflies of genera Diprion and Neodiprion).

Coleoptera scarabaeidae, (4S)-метилоктановой кислоты − компонента агрегационного феромона жука-носорога рода Oryctes, (14S)-метилоктадец-1-ена − полового феромона персиковой минирующей моли Lyonetia clerkella, продемонстрированы новые возможности синтетического использования (R)-4-ментен-3-она.