Chemistry Of Unique Chiral Olefins. 1. Synthesis, Enantioresolution, Circular Dichroism, And Theoretical Determination Of The Absolute Stereochemistry Of Trans- And Cis-1,1',2,2',3,3',4,4'-octahydro-4,4'-biphenanthrylidenes
Chemistry Of Unique Chiral Olefins. 1. Synthesis, Enantioresolution, Circular Dichroism, And Theoretical Determination Of The Absolute Stereochemistry Of Trans- And Cis-1,1',2,2',3,3',4,4'-octahydro-4,4'-biphenanthrylidenes
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DOI：
10.1021/ja970667u
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发表时间：
1997-08
影响因子：
15
通讯作者：
N. Harada;A. Saito;N. Koumura;H. Uda;B. D. Lange;W. Jager;H. Wynberg;B. Feringa
中科院分区：
文献类型：
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作者：
N. Harada;A. Saito;N. Koumura;H. Uda;B. D. Lange;W. Jager;H. Wynberg;B. Feringa
合成了独特的手性烯烃(E)-1，1‘，2，2‘，3，3‘，4，4‘-octahydro-4，4‘-biphenanthrylidene(1)及其(Z)-异构体2。当使用带有手性固定相的高效液相色谱Okamoto柱直接拆分这些化合物时，得到了光学纯的对映体。这些手性烯烃的CD光谱在1BB过渡区表现出很强的Cotton效应，反映了它们的强扭曲π-电子体系。用π电子自洽场/组态相互作用/偶极速度分子轨道方法对手性烯烃(M，M)-(E)-1和(M，M)-(Z)-2的CD和UV光谱进行了理论计算。由计算结果确定这些手性烯烃的绝对立体结构分别为[Cd(+)239.0]-(M，M)-(E)-1和[Cd(+)238.1]-(M，M)-(Z)-2。
Unique chiral olefins, (E)-1,1‘,2,2‘,3,3‘,4,4‘-octahydro-4,4‘-biphenanthrylidene (1) and its (Z)-isomer 2, were synthesized. When these compounds are directly enantioresolved by using the HPLC Okamoto column with a chiral stationary phase, optically pure enantiomers were obtained. The CD spectra of these chiral olefins exhibit very intense Cotton effects in the 1Bb transition region reflecting their strongly twisted π-electron systems. The CD and UV spectra of chiral olefins (M,M)-(E)-1 and (M,M)-(Z)-2 were theoretically calculated by the π-electron self-consistent field/configuration interaction/dipole velocity molecular orbital method. From the calculation results, the absolute stereostructures of these chiral olefins were theoretically determined to be [CD(+)239.0]-(M,M)-(E)-1 and [CD(+)238.1]-(M,M)-(Z)-2, respectively.