Macrocycles with one and more ent-beyerane skeletons were prepared by the reaction of 16,19-dihydroxyent-beyerane with several dibasic carboxylic acid chlorides. The structures of the synthesized compounds, namely, the number of ent-beyerane skeletons in the macrocycle, depended on the length of the polymethylene chain in the acid chloride. The molecular structures of two of the synthesized macrocycles were established by x-ray crystal structures.The number of publications on the synthesis of macrocyclic compounds has risen dramatically in the last 20 years. The interest in them is due to their ability to act as host molecules, often exhibiting highly selective molecular recognition of guests (ions) [1-3]. Native macrocycles isolated from plants or marine organisms were also described in the literature [4][5][6][7]. However, these compounds have little practical value despite their biological activity because they are isolated in minimal quantities from natural sources. In this respect synthetic macrocycles obtained from biologically active metabolites isolated from natural sources in tangible quantities are much more promising. Several such compounds are known, for example, synthetic macrocycles based on bile acids [8] and mono-[9, 10] and diterpenoids [11][12][13][14]. It is noteworthy that the first macrocycles containing two diterpenoid skeletons were obtained as side products from the synthesis of compounds in which two isosteviol (16-oxo-ent-beyeran-19-oic acid) diterpenoid molecules (1) were joined by diester and anhydride spacers [14]. In order to synthesize macrocycles based on this diterpenoid, we used a more rational approach, the so-called acid-chloride approach, which consisted of the reaction of fully reduced isosteviol, diol 2, with dibasic carboxylic acid chlorides. As it turned out, the structures of the products depended on that of the starting acid chloride, namely, on the length of the hydrocarbon chain between the C(O)Cl groups.The reaction of 2 (16,19-dihydroxy-ent-beyerane) with malonic acid dichloride gave in 9% yield a product with a molecular ion that corresponded to the mass of macrocycle 3. According to PMR data this macrocycle was not a pure compound but a mixture of the head-to-head 3a and head-to-tail 3b isomers. This was indicated by the presence of not a single multiplet