取代基对手性唑噁唑硼烷催化还原苯基乙基酮对映体选择性影响的理论研究 |
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引用本文: | 杨思娅,孙成科,林雪飞. 取代基对手性唑噁唑硼烷催化还原苯基乙基酮对映体选择性影响的理论研究[J]. 有机化学, 2003, 23(12): 1400-1406 |
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作者姓名: | 杨思娅 孙成科 林雪飞 |
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作者单位: | 1. 曲靖师范学院化学系,曲靖,655000 2. 曲靖师范学院化学系,曲靖,655000;北京师范大学化学系,北京,100875 |
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基金项目: | 云南省教育厅科研基金 (No.0 1 2 2 4 ) |
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摘 要: | 用AM1方法和过渡态理论研究了取代基对含侧链手性噁唑硼烷催化还原苯 基乙杂程逖≡裥缘挠跋欤扑憬峁砻鳎杂逞≡裥匀【鲇?R)和(S)两个对映体?叫蟹从Φ乃俾食J龋盋(4)和C(5)位上的取代基呈顺式时,所得对映体以(R) 型为主.对映选择性的高低与噁唑硼烷环上不同位置原子连接的取代基基团的大?∮泄兀扑憬峁胧笛樽芙岢龅慕崧巯辔呛希?$601 $AThe influence of substituents on the enantioselectivity in asymmetric branched-oxazaborolidine-catalyzed reductions of phenyl- ethyl ketone has been studied by using AMI MO method and transition state theory. The results show that the enantioselectivity is determined by the ratio of the rate constants of two parallel reactions conducting to spatial configurations (R) and (S). When the substituents connecting with C(4) and C(5) are in cis-form the reduction products of phenyl-ethyl ketone in the reactions are mainly of configuration ( R). In asymmetric boron-catalyzed reduction reactions the higher or lower magnitude for enantioselectivity and reaction barrier are governed by various substituents connecting with atoms of oxazaborolidine ring. The computational results are in consistence with experiments.
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关 键 词: | 过渡态理论 苯基乙基酮 恶唑硼烷 对映体 选择性 |
修稿时间: | 2003-04-08 |
Theoretical Study on the Influence of Substituents on Enantioselecthity in Branched-Oxazaborolidine-Catalyzed Reductions of Phenyl-ethyl Ketone |
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Affiliation: | Department of Chemistry,Qujing Normal College |
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Abstract: | The influence of substituents on the enantioselectivity in asymmetric branched oxazaborolidine catalyzed reductions of phenyl ethyl ketone has been studied by using AM1 MO method and transition state theory. The results show that the enantioselectivity is determined by the ratio of the rate constants of two parallel reactions conducting to spatial configurations (R) and (S) . When the substituents connecting with C(4) and C(5) are in cis form the reduction products of phenyl ethyl ketone in the reactions are mainly of configuration (R) . In asymmetric boron catalyzed reduction reactions the higher or lower magnitude for enantioselectivity and reaction barrier are governed by various substituents connecting with atoms of oxazaborolidine ring. The computational results are in consistence with experiments. |
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Keywords: | substituent phenyl ethyl ketone oxazaborolidine catalyzed enantioselectivity AM1 |
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