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Current Organic Chemistry

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ISSN (Print): 1385-2728
ISSN (Online): 1875-5348

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Research Article

Synthesis of Unsaturated Esters by Cross-Metathesis of Terpenes and Natural Rubber Using Ru-Alkylidene Catalysts

Author(s): Araceli Martínez*, Mikhail A. Tlenkopatchev, Selena Gutiérrez, Manuel Burelo, Joel Vargas and Enrique Jiménez-Regalado

Volume 23, Issue 12, 2019

Page: [1356 - 1364] Pages: 9

DOI: 10.2174/1385272823666190723125427

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Abstract

This study reports the cross-metathesis of bicyclic β-pinene, acyclic cis-3- methylpent-2-ene terpenes and the natural rubber with functionalized olefins, a route for the functionalization of the carbon-carbon double bond of natural products to obtain aliphatic unsaturated esters. The production of unsaturated esters from β-pinene and cis-3- methylpent-2-ene via cross-metathesis reaction with dimethyl maleate and diethyl maleate in the presence of the ruthenium-alkylidene [Ru(Cl)2(=CHPh)(1,3-bis(2,4,6- trimethylphenyl)-2-imidazolidinylidene)(PCy3)] (I), [Ru(Cl)2(=CH(o-isopropoxyphenylmethylene))( 1,3-bis(2,4,6-trimethylphenyl) -2-imidazolidinylidene)] (II) and rutheniumvinylidene [RuCl2(=C=CH(p-C6H4CF3))(PCy3)2] (III) was carried out. Results showed that the reaction of β-pinene with diethyl maleate using II catalyst produced unsaturated esters with 43 % selectivity. I and III catalysts showed low activity toward the cross-metathesis of β-pinene and dimethyl maleate. A survey about the cross-metathesis of acyclic cis-3-methylpent-2-ene with diethyl maleate by II catalyst was also studied. The formation of ethyl but-2-enoate and ethyl-3-methylpent-2-enoate products was highly selective by 63 %. The unsaturated esters formation from the cross-metathesis degradation of natural rubber (99.9 % cis-polyisoprene) with dimethyl maleate and diethyl maleate using I-III catalysts was accomplished as well. I and II catalysts showed high activity in the degradation of natural rubber with diethyl maleate to produce the low molecular weight of oligomers unsaturated ester products (Mn = 1 x 103 g mol-1) with isoprene units of m = 10 – 27 and yields ranging from 68 to 94 %.

Keywords: Cross-metathesis, β-pinene, natural rubber degradation, terpenes, unsaturated esters, ruthenium-alkylidene, functionalized olefins.

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