21856-96-2Relevant academic research and scientific papers
The Halogen–Samarium Exchange Reaction: Synthetic Applications and Kinetics
Anthore-Dalion, Lucile,Benischke, Andreas D.,Wei, Baosheng,Berionni, Guillaume,Knochel, Paul
supporting information, p. 4046 - 4050 (2019/02/26)
Fast I/Sm and Br/Sm exchanges take place when various aromatic or heterocyclic iodides and bromides are treated with nBu2SmCl?4 LiCl and nBu3Sm?5 LiCl, respectively. The resulting organosamarium reagents were efficiently quenched with aldehydes, ketones, and imines. Also, they undergo acylations when treated with N,N-dimethylamides leading to ketones. The rate of the Br/Sm exchange for a typical aryl bromide was determined and found to be 8.5×105 faster than the Br/Mg exchange, indicating that the rate of a metal-exchange is related to the ionic character of the carbon–metal bond and to the metal electronegativity.
An Efficient Ga(OTf)3/Isopropanol Catalytic System for Direct Reduction of Benzylic Alcohols
Sai, Masahiro
supporting information, p. 4330 - 4335 (2018/10/15)
This study aims to report the first gallium-catalyzed direct reduction of benzylic alcohols using isopropanol as a reductant. The reaction proceeds via gallium catalyst-assisted hydride transfer of the in situ-generated benzylic isopropyl ether. The method generates only water and acetone as byproducts and thus provides an atom-economic and environmentally friendly approach to the synthesis of di- and triarylmethanes, which are important substructures in various bioactive compounds and functional materials. (Figure presented.).
New and its salt cysteines compd.
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Paragraph 0122, (2016/12/22)
The purpose of the present invention is to provide a novel compound with Eg5 inhibiting activity that is useful as an antitumoral agent. The present invention pertains to a compound expressed by the general formula (I) (in formula (I), A represents Ch2, a
Synthesis and biological evaluation of l-cysteine derivatives as mitotic kinesin Eg5 inhibitors
Ogo, Naohisa,Oishi, Shinya,Matsuno, Kenji,Sawada, Jun-ichi,Fujii, Nobutaka,Asai, Akira
, p. 3921 - 3924 (2008/02/09)
Inhibition of Eg5 represents a novel approach for the treatment of cancer. Here, we report the synthesis and structure-activity relationship of S-trityl-l-cysteine (STLC) derivatives as Eg5 inhibitors. Some of these derivatives such as 4f demonstrated enh
Triaryl methane derivatives as antiproliferative agents
Al-Qawasmeh, Raed A.,Lee, Yoon,Cao, Ming-Yu,Gu, Xiaoping,Vassilakos, Aikaterini,Wright, Jim A.,Young, Aiping
, p. 347 - 350 (2007/10/03)
Clotrimazole (CLT) 1, a synthetic anti-fungal imidazole derivative, inhibits tumor cell proliferation and angiogenesis. In the current study, flow cytometric analysis demonstrated that the decrease in tumor cell growth by CLT 1 was associated with inhibition of cell cycle progression at the G 1-S phase transition, resulting in G0-G1 arrest. A series of CLT 1 analogues has been generated in order to develop CLT 1 derivatives that are devoid of the imidazole moiety which is responsible for the hepatoxicity associated with CLT 1 while retaining CLT 1 efficacy. The majority of these analogues demonstrate in vitro antiproliferative activity ranging from submicromolar to micromolar concentrations.
Palladium-catalyzed arylation of α,α-disubstituted arylmethanols via cleavage of a C-C or a C-H bond to give biaryls
Terao, Yoshito,Wakui, Hiroyuki,Nomoto, Michiyo,Satoh, Tetsuya,Miura, Masahiro,Nomura, Masakatsu
, p. 5236 - 5243 (2007/10/03)
The palladium-catalyzed arylation of α,α-disubstituted arylmethanols with aryl halides proceeds not only via C-H bond cleavage at the ortho-position, but also via cleavage of the sp2-sp3 C-C bond with the liberation of ketones (β-carbon elimination) to give the corresponding biaryls. Both reactions appear to occur through common arylpalladium(II) alcoholate intermediates. The results of systematic studies with respect to which C-C or C-H bond is preferentially cleaved in the arylation are reported. Among the important findings is the selective elimination of ortho-substituted aryl groups even from aryl(diphenyl)methanols due to steric reasons. Thus, various biaryls having ortho-substituents can be produced efficiently by treatment of the corresponding aryl(diphenyl or dimethyl)methanols with aryl bromides and chlorides.
Reactivities of triarylmethyl and diarylmethyl cations with azide ion investigated by laser flash photolysis. Diffusion-controlled reactions
McClelland, Robert A.,Kanagasabapathy,Banait, Narinder S.,Steenken, Steen
, p. 1009 - 1014 (2007/10/02)
By use of the technique of laser flash photolysis, rate constants kAz and ks have been directly measured for the reactions at 20 °C in acetonitrile-water (AN-W) solutions of varying composition of 18 triarylmethyl and 10 diarylmethyl cations with azide and solvent. The cations have ks that depend on substituent and vary from ~101 to ~107 s-1. For the more stable ions kAz also varies, increasing with decreased electron donation and also increasing by as much as 103 with increasing acetonitrile content. For less stable cations, however, the rate constant becomes independent of substituent. The break occurs when ks has reached ~105 s-1. The limiting rate constants have magnitudes in the vicinity of 1010 M-1 s-1; these do depend on solvent and type of cation, with diarylmethyl cations reacting at the limit 1.6 ± 0.2 times faster than triarylmethyl. The data can be fit by a model where there is diffusional encounter of the cation and azide to form an ion pair, with the combination within the ion pair rate-limiting for the more stable cations and the diffusion step rate-limiting for the less stable ones. The limiting rate constants represent the latter, diffusional encounter of the cation and azide. The Debye-Smoluchowski equation for diffusion-controlled reactions predicts rate constants that are larger than observed by factors of 2-2.5 for diarylmethyl and 4 for triarylmethyl. Deviations can be attributed to nonproductive encounters where the anion has approached the cation in the plane of one of the rings and thus cannot form a proper reacting configuration. The difference between the two types of cations is explained by the greater difficulty of achieving this configuration with the more sterically congested triarylmethyl cation. Ratios kAz/ks obtained from product analysis (competition kinetics) have previously been found to show adherence to the reactivity-selectivity principle. This has been interpreted (Rappoport, Jencks) in terms of the reaction with azide having reached the diffusion limit. The directly measured kAz establish that this is indeed the case. This study also validates the use of azide as a "clock" (Jencks, Richard) for converting such ratios to absolute rate constants through use of a value of 5 × 109 M-1 s-1 for kAz. The directly measured diffusion-limited kAz are somewhat larger than this, but the differences are small, at most a factor of 4.
Aggregation of Trityl Ions in an Acid Medium
Dickert, F. L.,Fritsch, K. D.,Bauer, G. R.,Mages, G.
, p. 1 - 10 (2007/10/02)
In concentrations larger than 1 M triphenyl carbenium ions associate in trifluoroacetic acid in spite of their coulombic repulsion.This phenomenon depends extremely strong on concentration.Astonishingly a separate NMR signal is found for the aggregate whe
