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.

The first syntheses of 9‐J1‐phytoprostane and 9‐A1‐phytoprostane methyl ester were achieved enantioselectively using a divergent approach from a common intermediate sulfone 4. The divergence was accomplished using a sigmatropic rearrangement (swap protocol) to give sulfone 5 in 47 % overall yield. The two upper side‐chains, with a stereodefined E double bond, were installed using consolidated Julia–Lythgoe olefination reactions of sulfones 4 and 5, with the same enantiopure α‐protected aldehyde 6.

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2-Chloro-, 2-bromo-, and 2-iodothiophenes undergo photochemical dehalogenation via the triplet state. In the presence of suitable π-bond nucleophiles, thienylation occurs with modest yield from chloro and bromo derivatives (via photogenerated triplet 2-thienyl cation). Specific trapping by using oxygen along with computational analysis carried out by means of a density functional method support that, in the case of iodo derivatives, homolytic thienyl-I bond fragmentation occurs first and heteroaryl cations are formed by electron transfer within the triplet radical pair, thus opening an indirect access to such cations.

A Divergent Enantioselective Synthesis of 9-J 1-Phytoprostane and 9-A1-Phytoprostane Methyl Ester. -(PORTA*, A.; CHIESA, F.; QUARONI, M.; PERSICO, M.; MORATTI, R.; ZANONI, G.; VIDARI, G.; Eur. J. Org. Chem. 2014, 10, 2111-2119, http://dx.