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
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
2012
发表期刊J. Org. Chem.
ISSN0022-3263
卷号77期号:4页码:1701-1709
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.
学科领域天然产物有机化学
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
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收录类别SCI
语种英语
WOS记录号WOS:000300340000010
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文献类型期刊论文
条目标识符http://ir.sioc.ac.cn/handle/331003/28609
专题中科院天然产物有机化学重点实验室
通讯作者Jiang B(姜标); ZHANG JOHN Z H
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GB/T 7714
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.
APA 姜标.,韩磊.,李永乐.,赵小龙.,雷洋.,...&ZHANG JOHN Z H.(2012).Combined Theoretical and Experimental Study on High Diastereoselective Chirality Transfer Based on [2.2]Paracyclophane Derivative Chiral Reagent.J. Org. Chem.,77(4),1701-1709.
MLA 姜标,et al."Combined Theoretical and Experimental Study on High Diastereoselective Chirality Transfer Based on [2.2]Paracyclophane Derivative Chiral Reagent".J. Org. Chem. 77.4(2012):1701-1709.
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