Naturalproductman’s Blog

Hey, is that a natural product?!

Archive for the ‘Cubitane’ Category

Cubitane Synthesis

Posted by naturalproductman on January 19, 2010

Thomas Lindel and co-workers at TU Braunschweig have recently published in Organic Letters on the enantioselective synthesis of a cubitane carbon skeleton that is a 12-membered macrocycle.  The method they used was the radical cyclization approach.  There is a carbon carbon bond cleavage involved that requires the introduction of an alpha-hydroperoxy group on a ketone followed by an alkyl shift, which leads to the generation of an oxacarbenium ion that gets hydrolyzed to yield the 12-membered macrocycle.  The alpha-hydroperoxy ketone intermediate is generated by treating the ketone with lithium aluminum hydride in ether for 2 days under air exposure.

cubitane
OL paper

Posted in C-C Bond Breaking, Cascade Reactions, Cubitane, Diterpenoids, Methodology, Peroxides, Radical Chemistry, Ring Opening | Leave a Comment »

 
Follow

Get every new post delivered to your Inbox.

Join 66 other followers