A unified stereodivergent strategy for prostaglandin and isoprostanoid synthesis.

Acetoxyfulvene surrended to asymmetric Diels-Alder cycloaddition, paving the way to the development of a unified strategy for the stereodivergent synthesis of both prostaglandins and isoprostanoids. In fact, the cycloadduct was subsequently converted to a common intermediate, which through two different stereoselective pathways afforded the two lactones 1 and 2, which are key building blocks in the synthesis of prostaglandins and isoprostanoids, respectively.

Stereodivergent strategy for neurofuran synthesis via palladium-catalyzed asymmetric allylic cyclization: total synthesis of 7-epi-ST-Δ(8)-10-neurofuran.

Neurofurans are formed in vivo in the human brain as a consequence of an increased oxidative stress, and they could be valuable biomarkers of the neuronal oxidative stress. In this paper, an enantioselective stereodivergent approach to two key neurofuran precursors, belonging to the AC and ST classes, has been developed starting from a single achiral precursor, the meso-diol 11. The absolute configuration of the THF cores was secured by a Pd-catalyzed asymmetric allylic alkylation using (S,S)-L1 and (R,R)-L2 ligands, respectively.

Improved synthesis of (E)-12-nitrooctadec-12-enoic acid, a potent PPARγ activator. Development of a "buffer-free" enzymatic method for hydrolysis of methyl esters.

Endogenous nitro-fatty acids, acting as partial agonist of PPARγ, are able to lower the insulin and glucose levels without the side effects associated with common antidiabetic drugs. (E)-12-Nitrooctadec-12-enoic acid, a potent activator of this peroxisome receptor, was synthesized in a very efficient sequence via a Henry-retro-Claisen ring fragmentation, followed by a novel enzymatic cleavage of methyl esters. The latter method was then applied in the last step of the synthesis of a few labile natural products, such as prostaglandins, isoprostanes, and phytoprostanes.