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Notable and obvious ketene substituent-dependent effect of temperature on the stereoselectivity in the Staudinger reaction
Li, Bonan; Wang, Yikai; Du, Da-Ming; Xu, Jiaxi
Source PublicationJOURNAL OF ORGANIC CHEMISTRY
2007-02-02
DOI10.1021/jo0622734
Volume72Issue:3Pages:990-997
Indexed BySCI ; IC
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences
WOS SubjectChemistry, Organic
WOS Research AreaChemistry
WOS KeywordBETA-LACTAM ANTIBIOTICS ; IMINE CYCLOADDITION REACTION ; ASYMMETRIC-SYNTHESIS ; STEREOSPECIFIC SYNTHESIS ; STEREOCONTROLLED SYNTHESIS ; CYCLO-ADDITIONS ; MECHANISM ; DERIVATIVES ; CHLORIDE ; STEREOCHEMISTRY
AbstractA 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.
Language英语
WOS IDWOS:000243735500039
Citation statistics
Cited Times:67[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/140475
Collection中国科学院大连化学物理研究所
AffiliationPeking Univ, BNLMS, Key Lab Bioorgan Chem & Mol Engn, Minist Educ,Coll Chem & Mol Engn, Beijing 100871, Peoples R China
Recommended Citation
GB/T 7714
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.
APA Li, Bonan,Wang, Yikai,Du, Da-Ming,&Xu, Jiaxi.(2007).Notable and obvious ketene substituent-dependent effect of temperature on the stereoselectivity in the Staudinger reaction.JOURNAL OF ORGANIC CHEMISTRY,72(3),990-997.
MLA Li, Bonan,et al."Notable and obvious ketene substituent-dependent effect of temperature on the stereoselectivity in the Staudinger reaction".JOURNAL OF ORGANIC CHEMISTRY 72.3(2007):990-997.
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