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题名: Notable and obvious ketene substituent-dependent effect of temperature on the stereoselectivity in the Staudinger reaction
作者: Li, Bonan;  Wang, Yikai;  Du, Da-Ming;  Xu, Jiaxi
刊名: JOURNAL OF ORGANIC CHEMISTRY
发表日期: 2007-02-02
DOI: 10.1021/jo0622734
卷: 72, 期:3, 页:990-997
收录类别: SCI ;  IC
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Organic
研究领域[WOS]: Chemistry
英文摘要: A notable and obvious ketene substituent-dependent effect of temperature on the stereoselectivity in the Staudinger reaction was observed. Most Staudinger reactions show concave Eyring plots characterized by two lines with an inversion point, following the principle of isoinversion. Their cis-selectivities decrease with increasing temperature. Reactions involving intramolecular p-pi and pi-pi interactions between the ketene substituents and imine C-substituents reveal protruding, S-shaped or straight-line Eyring plots. Their cis-selectivities increase with increasing temperature in a certain temperature region because such interactions enhance the cis-selectivity. Staudinger reactions involving cyclic imines with different ketenes clearly indicate that the temperature-dependent stereoselectivity is caused by the different rate increases of the direct ring closure, which are affected by the p-pi and pi-pi interactions between ketene substituents and imine C-substituents if they exist, and the isomerization of the zwitterionic intermediates generated from ketenes and imines during the change in the reaction temperature, not by the competition of the imine exo and endo attacks to the ketenes. Our results also indicate that nonlinear Eyring plots do not always reveal a change of the stereoselectivity-determining step. Thus, one should use them carefully to determine any changes in the stereoselectivity-determining step during the change in the reaction temperature.
关键词[WOS]: BETA-LACTAM ANTIBIOTICS ;  IMINE CYCLOADDITION REACTION ;  ASYMMETRIC-SYNTHESIS ;  STEREOSPECIFIC SYNTHESIS ;  STEREOCONTROLLED SYNTHESIS ;  CYCLO-ADDITIONS ;  MECHANISM ;  DERIVATIVES ;  CHLORIDE ;  STEREOCHEMISTRY
语种: 英语
WOS记录号: WOS:000243735500039
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/140475
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Peking Univ, BNLMS, Key Lab Bioorgan Chem & Mol Engn, Minist Educ,Coll Chem & Mol Engn, Beijing 100871, Peoples R China

Recommended Citation:
Li, Bonan,Wang, Yikai,Du, Da-Ming,et al. Notable and obvious ketene substituent-dependent effect of temperature on the stereoselectivity in the Staudinger reaction[J]. JOURNAL OF ORGANIC CHEMISTRY,2007,72(3):990-997.
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