The cross-metathesis of methyl oleate with c/s-2-butene-1,4-diyl diacetate and the influence of protecting groups

Abstract

Background: α,ω-Difunctional substrates are useful intermediates for polymer synthesis. An attractive, sustainable and selective (but as yet unused) method in the chemical industry is the oleochemical cross-metathesis with preferably symmetric functionalised substrates. The current study explores the cross-metathesis of methyl oleate (1) with cis-2-butene-1,4-diyl diacetate (2) starting from renewable resources and quite inexpensive base chemicals. Results: This cross-metathesis reaction was carried out with several phosphine and N-heterocyclic carbene ruthenium catalysts. The reaction conditions were optimised for high conversions in combination with high cross-metathesis selectivity. The influence of protecting groups present in the substrates on the necessary catalyst loading was also investigated. Conclusions: The value-added methyl 11-acetoxyundec-9-enoate (3) and undec-2-enyl acetate (4) are accessed with nearly quantitative oleochemical conversions and high cross-metathesis selectivity under mild reaction conditions. These two cross-metathesis products can be potentially used as functional monomers for diverse sustainable polymers. © 2011 Behr and Pérez Gomes; licensee Beilstein-Institut.