Previously unknown ring closing metathesis reactions of diynes are described which open an efficient and stereoselective entry into macrocyclic (Z)-alkenes if the resulting cycloalkyne products are subjected to Lindlar reduction. This new two-step strategy offers significant advantages in stereochemical terms over conventional RCM of dienes which usually leads to (E,Z)-mixtures when applied to the formation of large rings. The tungsten alkylidyne complex (tBuO)3W⋮CCMe3(1a) and analogues thereof as well as a structurally unknown species formed in situ from Mo(CO)6 and p-chlorophenol effect the crucial alkyne metathesis reactions in a highly efficient manner, with the former catalyst being more tolerant toward structural variations of the substrates and polar functional groups. Applications to the stereoselective synthesis of the olfactory compounds ambrettolide 23 and yuzu lactone 24, the insect repellent azamacrolides epilachnene 31 and homoepilachnene 33, as well as to the fully functional building block 64 required for a total synthesis of the cytotoxic alkaloid nakadomarin A 51 highlight the relevance of this new concept for natural product chemistry. In the latter case, the diyne substrate 62 necessary for ring closing alkyne metathesis was obtained via a novel furan synthesis relying on a palladium-catalyzed opening of a vinyl epoxide followed by an oxidative cyclization of the heterocyclic ring
The present work analyzes and compares the carbon dioxide absorption process in aqueous solutions of different amines (MEA, monoethanolamine; DEA, diethanolamine; TEA, triethanolamine). This study evaluates the influence of the reagents nature upon absorption using a semicontinuous regime in a bubble contactor. 13 C and 1 H nuclear magnetic resonance (NMR) spectroscopy has been used to analyze species (reagents and/or products) in the reaction medium. In this way, the influence of the amino group substitution degree and carbon dioxide loading upon the chemical absorption mechanism were analyzed.
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