7693-39-2Relevant academic research and scientific papers
Stereochemical outcomes of C–F activation reactions of benzyl fluoride
Champagne, Pier Alexandre,Desroches, Justine,Keddie, Neil S.,O'Hagan, David,Paquin, Jean-Fran?ois
supporting information, p. 106 - 113 (2020/05/06)
In recent years, the highly polar C–F bond has been utilised in activation chemistry despite its low reactivity to traditional nucleophiles, when compared to other C–X halogen bonds. Paquin's group has reported extensive studies on the C–F activation of benzylic fluorides for nucleophilic substitutions and Friedel–Crafts reactions, using a range of hydrogen bond donors such as water, triols or hexafluoroisopropanol (HFIP) as the activators. This study examines the stereointegrity of the C–F activation reaction through the use of an enantiopure isotopomer of benzyl fluoride to identify whether the reaction conditions favour a dissociative (SN1) or associative (SN2) pathway. [2H]-Isotopomer ratios in the reactions were assayed using the Courtieu 2H NMR method in a chiral liquid crystal (poly-γ-benzyl-L-glutamate) matrix and demonstrated that both associative and dissociative pathways operate to varying degrees, according to the nature of the nucleophile and the hydrogen bond donor.
Stereochemical outcomes of C-F activation reactions of benzyl fluoride
Keddie, Neil S.,Champagne, Pier Alexandre,Desroches, Justine,Paquin, Jean-Fran?ois,O'Hagan, David
supporting information, p. 106 - 113 (2018/02/06)
In recent years, the highly polar C-F bond has been utilised in activation chemistry despite its low reactivity to traditional nucleophiles, when compared to other C-X halogen bonds. Paquin's group has reported extensive studies on the C-F activation of benzylic fluorides for nucleophilic substitutions and Friedel-Crafts reactions, using a range of hydrogen bond donors such as water, triols or hexafluoroisopropanol (HFIP) as the activators. This study examines the stereointegrity of the C-F activation reaction through the use of an enantiopure isotopomer of benzyl fluoride to identify whether the reaction conditions favour a dissociative (SN1) or associative (SN2) pathway. [2H]-Isotopomer ratios in the reactions were assayed using the Courtieu 2H NMR method in a chiral liquid crystal (poly-γ-benzyl-L-glutamate) matrix and demonstrated that both associative and dissociative pathways operate to varying degrees, according to the nature of the nucleophile and the hydrogen bond donor.
ORIGINAL REACTIONS OF α,α-DITHIO ARYL ALKANES WITH BUTYLLITHIUMS
Krief, Alain,Kenda, Benoit,Barbeaux, Philippe
, p. 2509 - 2512 (2007/10/02)
Thioacetals derived from aromatic ketones react with butyllithiums already at -78 deg C and produce via a reductive process the corresponding α-thiobenzyllithiums in high yields.The same reaction also takes place selectively, under suitable conditions, wi
The synthesis and some application of new 1,3-dilithiopropanes: dimethylbis(α-lithiobenzyl)silane and its germanium analogue
Akkerman, O. S.,Bickelhaupt, F.
, p. 159 - 168 (2007/10/02)
The dimethylbis(α=lithiobenzyl)silanes and -germanes were prepared by the reaction of dimethylbis(α-thiophenylbenzyl)silane or -germane with lithium dispersion and their reactions with Me3M'Cl (M'=Ge, Sn) investigated.The lithium compounds proved to be useful in the synthesis of 2,4-diphenyl-substituted 1,3-disila-, 1,3-digerma- and 1-germa-3-silacyclobutanes.
