title: Highly stereoselective synthesis of cyclopentanes bearing four stereocentres by a rhodium carbene-initiated domino sequence.
abstract: Stereoselective synthesis of a cyclopentane nucleus by convergent annulation constitutes a significant challenge for synthetic chemists. Although a number of biologically relevant cyclopentane natural products are known, more often than not, the cyclopentane core is assembled in a stepwise manner because of the lack of efficient annulation strategies. Here we report the rhodium-catalysed reactions of vinyldiazoacetates with (E)-1,3-disubstituted 2-butenols generate cyclopentanes, containing four new stereogenic centres with very high levels of stereoselectivity (99% ee, >97: 3 dr). The reaction proceeds by a carbene-initiated domino sequence consisting of five distinct steps: rhodium-bound oxonium ylide formation, [2,3]-sigmatropic rearrangement, oxy-Cope rearrangement, enol-keto tautomerization and finally an intramolecular carbonyl ene reaction. A systematic study is presented detailing how to control chirality transfer in each of the four stereo-defining steps of the cascade, consummating in the development of a highly stereoselective process.
authors.affiliation: Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, USA.
authors.forename: Brendan T
authors.initials: BT
authors.lastname: Parr
authors.affiliation: Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, USA.
authors.forename: Huw M L
authors.initials: HM
authors.lastname: Davies
mesh_terms: D000438:Alcohols / Q000737:chemistry; D002384:Catalysis; D003517:Cyclopentanes / Q000138:chemical synthesis*; D003979:Diazonium Compounds / Q000737:chemistry; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000737:chemistry
chemical_list: D000438:Alcohols; D003517:Cyclopentanes; D003979:Diazonium Compounds; D014753:Vinyl Compounds; C030011:carbene; D012238:Rhodium; D008697:Methane
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