Total synthesis of C19 lipid diols containing a 2,5-disubstituted-3-oxygenated tetrahydrofuran

Abstract

The total synthesis of the C(19) lipid diols 5 and 6, the enantiomers of the anthelmintic marine natural products 1 and 3, is described. Key steps in the divergent syntheses include a syn selective epoxidation of a homoallylic alcohol, a one-pot alkoxypalladation-carbonylation-lactonisation reaction sequence and a DMEAD promoted Mitsunobu inversion.

Oxidative Carbonylation as a Powerful Tool for the Direct Synthesis of Carbonylated Heterocycles

“…[28] Palladium-catalysed oxidative heterocyclization/intramolecular alkoxycarbonylation of alk-4-ene-1,2-diols, alk-5ene-1,2-diols and related substrates represents a useful approach to bis-heterocyclic lactones (Scheme 27). [30] The enantioselective version of the oxidative oxycarbonylation of 4-ene-1,2-diols has also recently been achieved by kinetic resolution in the presence of nonracemic bis-oxazoline ligands. [30] The enantioselective version of the oxidative oxycarbonylation of 4-ene-1,2-diols has also recently been achieved by kinetic resolution in the presence of nonracemic bis-oxazoline ligands.…”

Total Synthesis of (+)-Panacene

“…The total synthesis of the naturally occurring enantiomer, (+)-panacene ( 1 ), has not yet been reported. Our continuing interest in both the development of synthetic methods for the construction 2,5-disubsituted-3-oxygenated tetrahydrofurans and brominative cyclizations impelled us to undertake the total synthesis of (+)-panacene ( 1 ), which is described in this Letter .…”

Advances in Total Synthesis of Some 2,3,5‐Trisubstituted Tetrahydrofuran Natural Products

“…Since the THF formation was stereocontrolled by correct stereochemistry of reacting groups for milder intramolecular S N 2 displacement (rather than epoxide formation), the synthesis was quite efficient and led to the oxylipids (3 a and 3 b) in just 6 steps and 37% and 26% overall yields, respectively. Nesbitt and McErlean [78] in accomplished the synthesis of three diastereomeric oxylipids through epoxidation of homoallylic alcohol, Pd-catalyzed carbonylative-lactonization and Mitsunobu inversion (Scheme 28). Their synthesis began with epoxidation of homoallyl alcohol 185 to deliver inseparable mixture (1 : 2 dr) of epoxy alcohols, which on further treatment with sulfur ylide gave the homologated allyl alcohols 186 a and 186 b.…”