- Iron(II)-Catalyzed Intermolecular Aminofluorination of Unfunctionalized Olefins Using Fluoride Ion
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We herein report a new catalytic method for intermolecular olefin aminofluorination using earth-abundant iron catalysts and nucleophilic fluoride ion. This method tolerates a broad range of unfunctionalized olefins, especially nonstyrenyl olefins that are incompatible with existing olefin aminofluorination methods. This new iron-catalyzed process directly converts readily available olefins to internal vicinal fluoro carbamates with high regioselectivity (N vs F), many of which are difficult to prepare using known methods. Preliminary mechanistic studies demonstrate that it is possible to exert asymmetric induction using chiral iron catalysts and that both an iron-nitrenoid and carbocation species may be reactive intermediates.
- Lu, Deng-Fu,Zhu, Cheng-Liang,Sears, Jeffrey D.,Xu, Hao
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supporting information
p. 11360 - 11367
(2016/10/12)
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- Barriers to Internal Rotation in 1,3,5-Trineopentylbenzenes.10. 13C and 19F NMR Band Shape Studies and Force Field Calculations.
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1,3,5-Trineopentylbenzenes (TNB) with one or two benzylic substituents in each neopentyl group were synthesized.The substituents were F, Cl, Br, I, OCH3, OCOCH3, OSi(CH3)3 and CH3 and, in cases of disubstitution, F, Cl, Br, CH3 and Cl, CH3 and Br and -SCH2CH2S-.Barriers to internal Csp3-Csp2 (aryl) and Csp3-Csp3 rotation were estimated by 13C and 19F NMR band shape methods.Estimated barriers in the TNB series were found to be very close to those found for the corresponding mononeopentylbenzenes.For some of the compounds studied, molecular mechanics (MM) calculations were performed with the Allinger MMP1 program.Differ ences between calculated and experimental estimated barriers were found, and possible sources of these discrepancies in terms of parameters used in the MMP1 program are discussed.
- Andersson, Sven,Drakenberg, Torbjoern
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p. 602 - 615
(2007/10/02)
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- (POLYFLUOROALKOXY)-N,N-DIALKYLAMINOFLUOROSULFURANES AND TRIS(POLYFLUOROALKOXY)-N,N-DIALKYLAMINOSULFURANES
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(Polyfluoroalkoxy)-N,N-dialkylaminodifluorosulfuranes, bis(polyfluoroalkoxy)-N,N-dialkylaminofluorosulfuranes, and tris(polyfluoroalkoxy)-N,N-dialkylaminosulfuranes were obtained by the reaction of N,N-dialkylaminotrifluorosulfuranes with trimethylsilyloxypolyfluoroalkanes.
- Markovskii, L. N.,Bobkova, L. S.,Pashinnik, V. E.
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p. 1699 - 1703
(2007/10/02)
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