Influence of the rigid spacer to macrocyclization of poly(thialactones): synthesis and computational analysis

Formation of macrocyclic lactones 8‐19 by ring‐opening condensation of corresponding stannathianes 1‐4 with diacyl dichlorides 5‐7 was studied experimentally and theoretically. The cyclization reactions afforded mixtures of corresponding monomers (M), dimers (D), and trimers (T). In order to rationa...

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Published in:Journal of physical organic chemistry 2009-05, Vol.22 (5), p.431-437
Main Authors: Vujasinović, Ines, Mlinarić-Majerski, Kata, Bertoša, Branimir, Tomić, Sanja
Format: Article
Language:English
Subjects:
adamantane
macrocyclization
poly(thialactones)
polycyclic compounds
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Summary:Formation of macrocyclic lactones 8‐19 by ring‐opening condensation of corresponding stannathianes 1‐4 with diacyl dichlorides 5‐7 was studied experimentally and theoretically. The cyclization reactions afforded mixtures of corresponding monomers (M), dimers (D), and trimers (T). In order to rationalize the influence of type and size of the spacer on the products ratio in the M‐D‐T mixtures we performed a force field based molecular modeling study. Monte Carlo conformational search was conducted and lowest energy conformations in chloroform were determined. Results of the molecular modeling in combination with the assumed kinetic parameters enabled better understanding of the experimentally obtained composition of the M‐D‐T‐mixtures. Copyright © 2008 John Wiley & Sons, Ltd. Formation of macrocyclic lactones 8‐19 by ring‐opening condensation of corresponding stannathianes 1‐4 with diacyl dichlorides 5‐7 was studied experimentally and theoretically. The cyclization reactions afforded mixtures of corresponding monomers (M), dimers (D), and trimers (T). In order to rationalize the influence of type and size of the spacer on the products ratio in the M‐D‐T mixtures we performed a force field based molecular modeling study.
ISSN:0894-3230
1099-1395
DOI:10.1002/poc.1479