A highly convergent synthesis of (-)-okilactomycin is described. Key reactions of this synthesis include a strategy-level diastereoselective oxy-Cope rearrangement/oxidation sequence, a Petasis-Ferrier union/rearrangement tactic, and an efficient RCM reaction to construct the 13-membered macrocyclic ring.

A new method for the construction of quaternary centers on cycloalkane rings is reported. The Cope rearrangement of 4methyl-2-allyl-2-(N-pyrrolidinyl)-carboxamide-3-cyclohexenone yields 4-methyl-4allyl-2-(N-pyrrolidinyl)-carboxamide-2-cyclohexenone in high yield. The rearrangement substrates are easily generated from Birch reduction-allylation of o-anisic acid derivatives. © 2012 Elsevier Scien...

BACKGROUND The nature of the heteroatom substitution in the nitrogen of a 3-aza-Cope system is explored. RESULTS While N-propargyl isoxazolin-5-ones suffer 3-aza-Cope rearrangements at 60°C, the corresponding N-propargyl pyrazol-5-ones need a higher temperature of 180°C for the equivalent reaction. When the propargyl group is substituted by an allyl group, the temperature of the rearrangement...

The 2-Aza-Cope rearrangement of γ-alkenyl nitrones is a rare example of the neutral thermal 2-aza-Cope process that usually takes place with cationic species. During the rearrangement, a redistribution of bonds and electronic density occurs in one kinetic step. However, the introduction of substituents with different steric requirements and electronic features might alter the activation energie...