Stereoselective Methodologies for the Synthesis of Acyclic Polyisoprenoids
Pp. 1-80 (80)
Acyclic polyisoprenoids are ubiquitous in nature from bacteria to human
cells. Beside, their leading role as precursor of thousands of cyclic terpenoids, they
have also a tremendous importance as membrane constituents, protein modulators and
nanoparticle carrier material. Their synthesis is a main topic since the dawn of organic
chemistry, nevertheless today there is still no universal method to access these
compounds and it remains space for finding original and efficient solutions. In this
review we provided an overview of the synthetic methods available for the synthesis of
head-to-tail and tail-to-tail 1,5-diene-containing polyprenyl derivatives, including
alkylation reactions of organometallics and heteroatom stabilized carbanions,
sigmatropic rearrangements, transition metal catalyzed methods and also biocatalytic
syntheses. The synthesis of small difunctionnal building blocks from cheap naturally
occurring polyprenols such as geraniol or farnesol are described. A special emphasis
will be given on the coupling of polyisoprenoid chains to carbocycles including
synthesis of isoprenoid quinones.
Allylic Reductive Coupling, Bielmann-Ducep Coupling, Coenzyme
Q10, 1, 5-Dienes, Farnesol, Geraniol, Geranylgeraniol, Isoprene, Menaquinone,
Olefin Formation, Polyprenols, Polyisoprenoids, Polyprenyl Quinones, Shapiro
Reaction, Solanesol, Stereoselectivity, Squalene, Suzuki-Miyaura Cross Coupling,
Terpenes, Trisubstituted Double Bond, Vitamin K, Wittig Reaction.
Institut Galien Paris-Sud, UMR 8612, CNRS, Universite Paris-Saclay, Faculte de Pharmacie, Chatenay-Malabry, France.