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学科主题: 天然产物有机化学
题名: Combined Theoretical and Experimental Study on High Diastereoselective Chirality Transfer Based on [2.2]Paracyclophane Derivative Chiral Reagent
其他题名: Combined Theoretical and Experimental Study on High Diastereoselective Chirality Transfer Based on [2.2]Paracyclophane Derivative Chiral Reagent
作者: Jiang B(姜标) ; Han L(韩磊) ; Li YL(李永乐) ; Zhao XL(赵小龙) ; Lei Y(雷洋) ; XIE DAIQIAN ; ZHANG JOHN Z H
通讯作者: 姜标 ; ZHANG JOHN Z H
刊名: J. Org. Chem.
发表日期: 2012
卷: 77, 期:4, 页:1701-1709
收录类别: SCI
部门归属: 中科院上海有机化学研究所; 南京大学; 华东师范大学
英文摘要: We report a paracyclophane N-Me thioamide chiral reagent for the asymmetric thio-Claisen rearrangement with high diasteroselectivity. Comparisons between candidate chiral reagent N-phenyl-N-([2.2]paracyclophan-4-yl)amide, N-methyl amide, N-phenyl thioamide, and N-methyl thioamide are made both by experiment and theoretical calculations to clarify the principle behind the high diasteroselectivity. Dynamic H-1 NMR phenomenon tested by varying temperature (VT) experiments has proved that N-Ph amides have triple splitting peaks, while N-Ph thioamide would reduce the number to two, further substituting the Ph to Me made dynamic phenomenon disappear. So the side chain is thought to be the most rigid in N-Me thioamide, which accounts for a structure prerequisite favoring high efficient chirality transfer. This is confirmed by theoretical calculation: remarkable energy difference exists between the Re and Si faces of the chiral molecule. To further clarify the possible pathways for thio-Claisen rearrangement, theoretical prediction is adopted. The result implies that the cisoid pathways will dominate the process. Further experiment confirmed this: with N-Me thioamide, the asymmetrical reaction affords gamma-unsaturated thioamides in good yields and high diastereoselectivities up to 98%. After removing the thioamide auxiliaries under hydrolysis conditions, product beta,gamma-substituted chiral alcohols reached high enantiopurity of 98% ee.
语种: 英语
相关网址: 查看原文
WOS记录号: WOS:000300340000010
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内容类型: 期刊论文
URI标识: http://ir.sioc.ac.cn/handle/331003/28609
Appears in Collections:中科院天然产物有机化学重点实验室_期刊论文

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Recommended Citation:
Jiang B,Han L,Li YL,et al. Combined Theoretical and Experimental Study on High Diastereoselective Chirality Transfer Based on [2.2]Paracyclophane Derivative Chiral Reagent[J]. J. Org. Chem.,2012,77(4):1701-1709.
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