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General Reaction Mode of Hypervalent Iodine Trifluoromethylation Reagent: A Density Functional Theory Study
Alternative Title高碘三氟甲基化试剂 (Togni 试剂1)反应模式的理论研究
Ling L(凌琳)1; Liu K(刘鲲)1; Li XQ(李鑫倩)1; Li YX(李玉学)1
2015
Source PublicationACS Catal.
Volume5Issue:4Pages:2458-2468
AbstractThe mechanisms of trifluoromethylation with hypervalent iodine trifluoromethylation reagent (Togni's reagent 1) have been comprehensively studied by density functional theory (DFT) calculations. The results show that there are two general reaction modes for reagent 1: (I) Mode-A, acting as a CF3 center dot free radical source. When one-electron reductants are available in the reaction system, such as Cu-I, Fe-II TEMPONa, or electron-rich lithium enolate, 1 will be reduced via single-electron transfer (SET) and give out CF3 center dot free radical concertedly. In the Cu-I-catalyzed trifluoromethylation of terminal olefins, Cu-I promotes the homo-cleavage of the F3C-I bond in 1 via SET to produce Cull species and CF3 center dot free radical. Then the CF3 center dot free radical attacks the olefin, leading to trifluoromethyl alkyl radical intermediate. Subsequently, the Cull species act as a one-electron oxidant oxidizing the alkyl radical to carbocation intermediate, and the following deprotonation leads to the final product. Other mechanisms, such as formation of F3C-Cu-III species via oxidative addition, formation of allylic radical intermediate, were considered and excluded. (II) Mode-B, acting as a CF3+ cation source. 1 can be activated by a Lewis acid such as Zn-II and becomes more inclined to undergo an S(N)2 type nudeophilic attack at the CF3 group by nucleophiles (pentanol in this work). For substrates studied in this paper, such as the lithium enolate, pentanol, and sodium 2,4,6-trimethylphenolate, the competition between their reducibility and nudeophilicity determines the reaction mode of regent 1.
Subtype论文
Subject Area金属有机化学
DOI10.1021/cs501892s
URL查看原文
Indexed BySCI
Language英语
WOS IDWOS:000352464400051
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Document Type期刊论文
Identifierhttp://ir.sioc.ac.cn/handle/331003/39590
Collection金属有机化学国家重点实验室
Corresponding AuthorLi YX(李玉学)
Affiliation1.中科院上海有机化学研究所, 金属有机化学国家重点实验室
2.天津师范大学
Recommended Citation
GB/T 7714
Ling L,Liu K,Li XQ,et al. General Reaction Mode of Hypervalent Iodine Trifluoromethylation Reagent: A Density Functional Theory Study[J]. ACS Catal.,2015,5(4):2458-2468.
APA 凌琳,刘鲲,李鑫倩,&李玉学.(2015).General Reaction Mode of Hypervalent Iodine Trifluoromethylation Reagent: A Density Functional Theory Study.ACS Catal.,5(4),2458-2468.
MLA 凌琳,et al."General Reaction Mode of Hypervalent Iodine Trifluoromethylation Reagent: A Density Functional Theory Study".ACS Catal. 5.4(2015):2458-2468.
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