title: Isotope effects and the nature of selectivity in rhodium-catalyzed cyclopropanations.
abstract: The mechanism of the dirhodium tetracarboxylate catalyzed cyclopropanation of alkenes with both unsubstituted diazoacetates and vinyl- and phenyldiazoacetates was studied by a combination of (13)C kinetic isotope effects and density functional theory calculations. The cyclopropanation of styrene with methyl phenyldiazoacetate catalyzed by Rh(2)(octanoate)(4) exhibits a substantial (13)C isotope effect (1.024) at the terminal olefinic carbon and a smaller isotope effect (1.003-1.004) at the internal olefinic carbon. This is consistent with a highly asynchronous cyclopropanation process. Very similar isotope effects were observed in a bisrhodium tetrakis[(S)-N-(dodecylbenzenesulfonyl)prolinate] (Rh(2)(S-DOSP)(4) catalyzed reaction, suggesting that the chiral catalyst engages in a very similar cyclopropanation transition-state geometry. Cyclopropanation with ethyl diazoacetate was concluded to involve an earlier transition state, based on a smaller terminal olefinic isotope effect (1.012-1.015). Density functional theory calculations (B3LYP) predict a reaction pathway involving complexation of the diazoesters to rhodium, loss of N(2) to afford a rhodium carbenoid, and an asynchronous but concerted cyclopropanation transition state. The isotope effects predicted for reaction of a phenyl-substituted rhodium carbenoid with styrene match within the error of the experimental values, supporting the accuracy of the theoretical calculations and the rhodium carbenoid mechanism. The accuracy of the calculations is additionally supported by excellent predictions of reaction barriers, stereoselectivity, and reactivity trends. The nature of alkene selectivity and diastereoselectivity effects in these reactions is discussed, and a new model for enantioselectivity in Rh(2)(S-DOSP)(4)-catalyzed cyclopropanations is presented.
authors.affiliation: Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842, USA.
authors.forename: Daniel T
authors.initials: DT
authors.lastname: Nowlan
authors.forename: Timothy M
authors.initials: TM
authors.lastname: Gregg
authors.forename: Huw M L
authors.initials: HM
authors.lastname: Davies
authors.forename: Daniel A
authors.initials: DA
authors.lastname: Singleton
mesh_terms: D000475:Alkenes / Q000737:chemistry; D001391:Azo Compounds / Q000737:chemistry; D002247:Carbon Isotopes; D002384:Catalysis; D003500:Cyclization; D003521:Cyclopropanes / Q000138:chemical synthesis* / Q000737:chemistry; D007700:Kinetics; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D001391:Azo Compounds; D002247:Carbon Isotopes; D003521:Cyclopropanes; D009942:Organometallic Compounds; D012238:Rhodium