Raising the ceiling of diastereoselectivity in hydrogen transfer on acyclic radicals.

We report here that the monodentate complexation of Me2AlCl to an ester group significantly enhances the selectivity of hydrogen transfer on acyclic radicals flanked by both an ester functionality and a stereogenic center, leading to C-2,C-3-anti products with high diastereoselectivity. In certain cases improved ratios were obtained using bulkier aluminum Lewis acid such as MAD (methylaluminum-di(di-2,6-tert-butyl-4-methylphenoxide). Electron spin resonance studies on these acyclic radicals indicate that Lewis acid complexation leads to conformational changes in the radicals. The stereochemistry of the preferred enolate radicals complexed with Lewis acids and their impact on the acyclic transition states involved are suggested.

Highly diastereoselective synthesis of decalin skeletons with quaternary carbon centers via the tandem oxy-Cope/ene/Claisen reaction.

The highly diastereoselective cascade sequence of three successive thermal pericyclic reactions of 1,2-divinylcyclohexanol allyl and propargyl ethers is described. This novel tandem process provides an efficient synthesis of sesqui- and diterpenoid skeletons having a quaternary carbon at C9. [reaction: see text]

Diastereoselective construction of quaternary carbons directed via macrocyclic ring conformation: formal synthesis of (-)-mesembrine.

In this article, we report a highly diastereoselective new method for the generation of quaternary carbon centers through an anionic oxy-Cope/alkylation sequence where the diastereoselectivity is induced by the conformation of a macrocyclic tetrasubstituted enolate. The use of our methodology culminated in the formal total synthesis of (-)-mesembrine (34) in 11 steps from known starting materials.