Selective isomerization-carbonylation of a terpene trisubstituted double bond

Hanna Busch (1) , Florian Stempfle (1) , Sandra Hess (1) , Etienne Grau (2, 3) , Stefan Mecking (1)

1 Univ Konstanz, Dept. Chemistry
2 LCPO - Laboratoire de Chimie des Polymères Organiques
3 Team 2 LCPO : Biopolymers & Bio-sourced Polymers

Selective catalytic carbonylation of the trisubstituted double bond of citronellic acid is enabled via an isomerization-functionalization approach. Alkoxycarbonylation with [{1,2-((Bu2PCH2)-Bu-t)(2)C6H4}Pd(OTf)(2)] as a catalyst precursor occurs with >97% selectivity for the terminal diester dimethyl-3,7-dimethylnonane-dioate. This prevails much over the typical cationic methonfaddition. The reactive primary carboxy group formed allows for e.g. the preparation of the high molecular weight novel polyester poly[3,7-dimethylnonanediyl-3,7-dimethylnonanedioate].

Mots clés: SYSTEMS; LIMONENE; OLEFINS; CATALYZED HYDROFORMYLATION; LINEAR ALDEHYDES; INTERNAL ALKENES; METHYL OLEATE; ACID ESTERS; METHOXYCARBONYLATION; MONOMERS

Domaines: Polymères; Catalyse; Chimie

Hanna Busch, Florian Stempfle, Sandra Hess, Etienne Grau, Stefan Mecking. Selective isomerization-carbonylation of a terpene trisubstituted double bond. Green Chemistry, 2014, 16 (10), pp.4541-4545. ⟨10.1039/c4gc01233j⟩. ⟨hal-01366463⟩