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Volumn , Issue 7, 2007, Pages 1091-1100

A mechanistic study on the catalytic, asymmetric α-bromination of acid chlorides

Author keywords

bromination; Asymmetric; Catalytic; Enantioselective

Indexed keywords


EID: 34250681402     PISSN: 1434193X     EISSN: 10990690     Source Type: Journal    
DOI: 10.1002/ejoc.200600819     Document Type: Article
Times cited : (22)

References (45)
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    • See Supporting Information for details
    • See Supporting Information for details.
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    • Molecular mechanics calculations confirm that there is a less than 0.5 kcal/mol difference between the diastereomeric acylammonium intermediates
    • Molecular mechanics calculations confirm that there is a less than 0.5 kcal/mol difference between the diastereomeric acylammonium intermediates.
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    • A combination of IMOMO (integrated molecular orbital + MO method) variation of ONIOM (n-layered integrated molecular orbital method) at the HF3-21G(d)//AM1 level, coupled with constrained Monte-Carlo conformational searches (MCMM) to generate initial IMOMO geometries.
    • A combination of IMOMO (integrated molecular orbital + MO method) variation of ONIOM (n-layered integrated molecular orbital method) at the HF3-21G(d)//AM1 level, coupled with constrained Monte-Carlo conformational searches (MCMM) to generate initial IMOMO geometries.
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    • The enolate carbon-bromine distances are 2.07 Å in TS1 and 2.09 Å in TS2. The quinone carbon-bromine distances are 2.69 Å in TS1 and 2.74 Å in TS2.
    • The enolate carbon-bromine distances are 2.07 Å in TS1 and 2.09 Å in TS2. The quinone carbon-bromine distances are 2.69 Å in TS1 and 2.74 Å in TS2.
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    • These bonds have measured distances of 2.26 Å, 2.41 Å, and 2.51 Å in TS1; and 2.28 Å, 2.29 Å, and 2.51 Å in TS2.
    • These bonds have measured distances of 2.26 Å, 2.41 Å, and 2.51 Å in TS1; and 2.28 Å, 2.29 Å, and 2.51 Å in TS2.
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    • f = +0.21 in TS2.
    • f = +0.21 in TS2.
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    • The ketene enolate oxygen-quinuclidine hydrogen distances are 2.37 Å and 2.51 Å in TS1 and, 2.36 Å and 2.51 Å in TS2.
    • The ketene enolate oxygen-quinuclidine hydrogen distances are 2.37 Å and 2.51 Å in TS1 and, 2.36 Å and 2.51 Å in TS2.
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    • Final energies represent ΔE values computed using the IMOMO method at the HF3-21G(d)//AM1 level. Reported Mulliken charges were determined at the B3LYP/6-31(d) level of theory through single-point calculations using optimized IMOMO geometries. Select hydrogens have been removed for simplicity.
    • Final energies represent ΔE values computed using the IMOMO method at the HF3-21G(d)//AM1 level. Reported Mulliken charges were determined at the B3LYP/6-31(d) level of theory through single-point calculations using optimized IMOMO geometries. Select hydrogens have been removed for simplicity.
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    • Among these are elongated quinone⋯Br bond lengths of 2.59 Å and 2.60 Å, and short enolate⋯Br distances of 2.17 Å and 2.18 Å, which are consistent with halogen transfer occurring late on the reaction coordinate.
    • Among these are elongated quinone⋯Br bond lengths of 2.59 Å and 2.60 Å, and short enolate⋯Br distances of 2.17 Å and 2.18 Å, which are consistent with halogen transfer occurring late on the reaction coordinate.
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    • Stochastic molecular dynamics simulations performed using the MMFFs force field as implemented in Macromodel 7.1. The plotted trajectories represent the average values obtained from 5 independent simulations conducted at 195.15 K and 1 atm in vacuo. Initial equilibration and minimizations were not performed due to the instability associated with transition state geometries being potential energy maxima on the reaction surface
    • Stochastic molecular dynamics simulations performed using the MMFFs force field as implemented in Macromodel 7.1. The plotted trajectories represent the average values obtained from 5 independent simulations conducted at 195.15 K and 1 atm in vacuo. Initial equilibration and minimizations were not performed due to the instability associated with transition state geometries being potential energy maxima on the reaction surface.
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    • Recent reviews of asymmetric epoxidation: a
    • Recent reviews of asymmetric epoxidation: a) C. L. Winn, V. K. Aggarwal, Acc. Chem. Res. 2004, 37, 611-620;
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    • Winn, C.L.1    Aggarwal, V.K.2
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    • Epoxide ee based on optical rotation. E. W. Collington, H. Finch, J. G. Montana, R. J. K. Taylor, J. Chem. Soc., Perkin Trans. 1 1990, 7, 1839-1843.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.