title: Diastereoselective rhodium-catalyzed ene-cycloisomerization reactions of alkenylidenecyclopropanes: total synthesis of (-)-α-kainic acid.
abstract: The rhodium-catalyzed ene-cycloisomerization of alkenylidenecyclopropanes provides an atom-economical approach to five-membered carbo- and heterocycles that contain two new stereogenic centers. A key and striking feature of this protocol is that the alkene geometry does not impact the efficiency and diastereocontrol, which provides excellent synthetic versatility. For instance, (E)- and (Z)-allylic alcohols furnish the corresponding aldehydes with similar efficiency and selectivity. This process facilitates the construction of a key intermediate in an eight-step total synthesis of (-)-α-kainic acid.
authors.affiliation: Department of Chemistry, The University of Liverpool, Crown Street, Liverpool L69 7ZD, United Kingdom. Andrew.Evans@liverpool.ac.uk
authors.forename: P Andrew
authors.initials: PA
authors.lastname: Evans
authors.forename: Phillip A
authors.initials: PA
authors.lastname: Inglesby
mesh_terms: D002384:Catalysis; D003500:Cyclization; D003521:Cyclopropanes / Q000737:chemistry*; D007608:Kainic Acid / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D003521:Cyclopropanes; D012238:Rhodium; D007608:Kainic Acid