The absolute configuration of antiinflammatory marine sesterterpenes belonging to the manoalide and cacospongionolide structural type has been determined by comparison of the CD spectra of the natural compounds with those of analogues that have been stereoselectively synthesized. In the derived acetates the relative stereochemistry of the stereogenic centres in the pyranofuranone moiety is assigned from 1H‐NMR data and the absolute configuration from CD spectra. The absolute configuration of the naturally occurring marine sesterterpenes thorectolide monoacetate, manoalide monoacetate, petrosaspongiolide M and cavernosolide has been determined.
Palladium complexes supported by tridentate phosphido diphosphine ligands (P(o-C 6 H 4 PR 2 ) 2 : 1, R ) i Pr; 2, R ) Ph) haVe been synthesized, characterized, and tested as catalysts for the electrophilic allylation of aldehydes. The palladium complex 2 resulted in an interesting catalyst for electrophilic allylation in the presence of allyltributyltin, giVing good yields under Very mild reaction conditions and eVen in the absence of the solVent.
Bishomoallylic alcohols are converted in good yields and diastereoselectivity into tetrahydrofuranols and tetrahydropyranols by Cp 2 TiCl 2 /t-butyl hydroperoxide/activated 4Å molecular sieves system.
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