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Updated: Apr 22, 2026

A Customizable Approach for the Enzymatic Production and Purification of Diterpenoid Natural Products
Published on: October 4, 2019
Promotion of selective pathways in isomerizing functionalization of plant oils by rigid framework substituents
Josefine T Christl1, Philipp Roesle, Florian Stempfle
1Department of Chemistry, University of Konstanz, 78464 Konstanz (Germany), Fax: (+49) 7531-88-5152.
Abstract:
The 1,2-(CH2 P(1-adamantyl)2 )2 C6 H4 (dadpx) coordinated palladium complex [(dadpx)Pd(OTf)2 ] (1) is a catalyst precursor for the isomerizing methoxycarbonylation of the internal double bond of methyl oleate, with an unprecedented selectivity (96 %) for the linear diester 1,19-dimethyl nonadecanedioate. Rapid formation of the catalytically active solvent-coordinated hydride species [(dadpx)PdH(MeOH)](+) (3-MeOH) is evidenced by NMR spectroscopy, and further isolation and X-ray crystal structure analysis of [(dadpx)PdH(PPh3 )](+) (3-PPh3 ). DFT calculations of key steps of the catalytic cycle unravel methanolysis as the decisive step for enhanced selectivity and the influence of the rigid adamantyl framework on this step by destabilization of transition states of unselective pathways.
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