典型文献
Computational insights into the effects of reagent structure and bases on nucleophilic monofluoromethylation of aldehydes
文献摘要：
Although fluorobis(phenylsulfonyl)methane(FBSM)and its cyclic analog 2-fluoro-1,3-benzodithiole-1,1,3,3-tetraoxide(FBDT)possess similar physicochemical properties,Shibata et al.found that FBSM failed to undergo nucleophilic monofluoromethylation of aldehydes regardless of the reaction conditions at-tempted(using various organic and inorganic bases).However,it was later discovered by Hu et al.that the nucleophilic monofluoromethylation could be accomplished by employing lithium hexamethyldisi-lazide(LiHMDS)as a base.Herein,we present an in-depth computational investigation into the intrigu-ing effects of reagent structure and bases on the nucleophilic monofluoromethylation of aldehydes.The computations reveal the 1,4-diazabicyclo[2.2.2]octane(DABCO)catalyzed nucleophilic monofluoromethy-lation of benzaldehyde with acyclic FBSM is a thermodynamically unfavorable process mainly due to the destabilizing O…O lone pair repulsions in FBSM product,whereas such repulsion could be largely avoided in FBDT product because of its constrained five-membered ring structure.Employing LiHMDS as a base can not only facilitate the nucleophilic monofluoromethylation via Li-O interactions but also render the monofluoromethylation of benzaldehyde with FBSM thermodynamically favored.
文献关键词：
中图分类号：
作者姓名：
Meng-Meng Zheng;Hao-Dong Tan;Yueqian Sang;Xiao-Song Xue;Jin-Pei Cheng
作者机构：
State Key Laboratory of Elemento-Organic Chemistry,College of Chemistry,Nankai University,Tianjin 300071,China;Key Laboratory of Organofluorine Chemistry,Shanghai Institute of Organic Chemistry,University of Chinese Academy of Sciences,Chinese Academy of Sciences,Shanghai 200032,China;Center of Basic Molecular Science,Department of Chemistry,Tsinghua University,Beijing 100084,China
文献出处：
引用格式：
[1]Meng-Meng Zheng;Hao-Dong Tan;Yueqian Sang;Xiao-Song Xue;Jin-Pei Cheng-.Computational insights into the effects of reagent structure and bases on nucleophilic monofluoromethylation of aldehydes)[J].中国化学快报（英文版）,2022(05):2387-2390
A类：
monofluoromethylation,fluorobis,phenylsulfonyl,benzodithiole,tetraoxide,FBDT,Shibata,hexamethyldisi,lazide,intrigu,diazabicyclo,monofluoromethy
B类：
Computational,insights,into,effects,reagent,structure,bases,nucleophilic,aldehydes,Although,methane,FBSM,its,analog,possess,similar,physicochemical,properties,found,that,failed,undergo,regardless,reaction,conditions,tempted,using,various,inorganic,However,was,later,discovered,by,Hu,could,accomplished,employing,lithium,LiHMDS,Herein,present,depth,computational,investigation,computations,reveal,octane,DABCO,catalyzed,benzaldehyde,acyclic,thermodynamically,unfavorable,process,mainly,due,destabilizing,lone,pair,repulsions,product,whereas,such,largely,avoided,because,constrained,five,membered,ring,Employing,can,not,only,facilitate,via,interactions,but,also,render,favored
AB值：
0.462988
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机标中图分类号，由域田数据科技根据网络公开资料自动分析生成，仅供学习研究参考。
