1623-07-0Relevant articles and documents
Nucleophilic 18F-fluorination of phosphorofluoridates and phosphonofluoridic acids via imidazole-activated precursors
Mou, Zhaobiao,Chen, Xueyuan,Wang, Chao,Wang, Tao,Yang, Hongzhang,Li, Zijing
supporting information, (2021/03/03)
18F-Labeled organofluorophosphates are important radiosynthons that have only been previously accessible via 18/19F-isotope-exchange with limited molar activities. Herein, a novel 18F-fluorination methodology has been developed to prepare 18F-labeled phosphorofluoridates and phosphonofluoridic acids via the [18F]F? nucleophilic substitution of imidazole-activated precursors. The efficient one-step 18F-fluorination affords stable products in the presence of Zn(Ⅱ) with high radiochemical yields and high molar activities. This 18F-fluorination method could be used to prepare various phosphorofluoridate and phosphonofluoridic acid analogs for use as 18F-radiosynthons and potential positron emission tomography tracers.
Dissociative reactions of benzonorbornadienes with tetrazines: Scope of leaving groups and mechanistic insights
Xu,Galindo-Murillo,Cheatham,Franzini
, p. 9855 - 9865 (2017/12/12)
Bioorthogonal dissociative reactions boast diverse potential applications in chemical biology and drug delivery. The reaction of benzonorbornadienes with tetrazines to release amines from carbamate leaving groups was recently introduced as a bioorthogonal bond-cleavage reaction. The present study aimed at investigating the scope of leaving groups that are compatible with benzonorbornadienes. Synthesis of several benzonorbornadienes with different releasable groups is reported, and the reaction of these molecules with tetrazine was found to be rapid and afforded high release yields. The tetrazine-induced release of molecules proceeds in a cascade of steps including inverse-electron demand cycloaddition and cycloreversion reactions that form unstable isoindoles/isobenzofuran intermediates and spontaneously eliminate a leaving group of interest. In the case of oxygen-bridged BNBDs at room temperature, we observed the formation of an unproductive byproduct.
Chemical pyrophosphorylation of functionally diverse peptides
Marmelstein, Alan M.,Yates, Lisa M.,Conway, John H.,Fiedler, Dorothea
supporting information, p. 108 - 111 (2014/01/23)
A highly selective and convenient method for the synthesis of pyrophosphopeptides in solution is reported. The remarkable compatibility with functional groups (alcohol, thiol, amine, carboxylic acid) in the peptide substrates suggests that the intrinsic nucleophilicity of the phosphoserine residue is much higher than previously appreciated. Because the methodology operates in polar solvents, including water, a broad range of pyrophosphopeptides can be accessed. We envision these peptides will find widespread applications in the development of mass spectrometry and antibody-based detection methods for pyrophosphoproteins.
One-pot synthesis of organophosphate monoesters from alcohols
Lira, Lucas M.,Vasilev, Dimitar,Pilli, Ronaldo A.,Wessjohann, Ludger A.
, p. 1690 - 1692 (2013/04/10)
A one-pot procedure for the phosphorylation of alcohols provides the corresponding phosphate monoesters in improved yields. The protocol features the use of tetrabutylammonium hydrogen phosphate and trichloroacetonitrile, followed by purification of the crude product by flash chromatography on silica gel. The final step, cation exchange chromatography, affords the organophosphates as ammonium salts that are usually required for biochemical applications. The mechanism appears to be phosphate rather than alcohol activation by trichloroacetonitrile.
Mono, di and tri-mannopyranosyl phosphates as mannose-1-phosphate prodrugs for potential CDG-Ia therapy
Hardre, Renaud,Khaled, Amira,Willemetz, Alexandra,Dupre, Thierry,Moore, Stuart,Gravier-Pelletier, Christine,Merrer, Yves Le
, p. 152 - 155 (2007/10/03)
An efficient and convergent method for the synthesis of mannose-1-phosphate prodrugs is described as a potential therapy for congenital disorders of glycosylation-Ia (CDG-Ia). The key feature of the proposed approach is the silver assisted nucleophilic substitution of 2,3,4,6-tetra-O-protected-α-d-mannopyranosyl bromides with various silver phosphate salts to afford mono, di, and tri-mannopyranosyl phosphates. A preliminary biological evaluation of the synthesized phosphate prodrugs has been carried out.
Regioselective phosphorylation of carbohydrates and various alcohols by bacterial acid phosphatases; probing the substrate specificity of the enzyme from Shigella flexneri
Van Herk, Teunie,Hartog, Aloysius F.,Van Der Burg, Alida M.,Wever, Ron
, p. 1155 - 1162 (2007/10/03)
Bacterial non-specific acid phosphatases normally catalyze the dephosphorylation of a variety of substrates. As shown previously the enzymes from Shigella flexneri and Salmonella enterica are also able to catalyze the phosphorylation of inosine to inosine monophosphate and D-glucose to D-glucose 6-phosphate (D-G6P) using cheap pyrophosphate as the phosphate donor. After optimization high yields (95%) are achieved in the latter reaction and we show here that it is possible to use these enzymes in a preparative manner. This prompted us to investigate by using 31P NMR and HPLC also the phosphorylation of a broad range of carbohydrates and alcohols. Many cyclic carbohydrates are phosphorylated in a regioselective manner. Non-cyclic carbohydrates are phosphorylated as well. Phosphorylation of linear alcohols, cyclic and aromatic alcohols is also possible. In all cases the acid phosphatase from Shigella prefers a primary alcohol function above a secondary one. We conclude that these enzymes are an attractive alternative to existing chemical and enzymatic methods in the phosphorylation of a broad range of compounds.
SAR directed design and synthesis of novel β(1-4)-glucosyltransferase inhibitors and their in vitro inhibition studies
Bhattacharya, Asish K,Stolz, Florian,Kurzeck, Juergen,Rueger, Wolfgang,Schmidt, Richard R
, p. 1129 - 1136 (2007/10/03)
This paper describes SAR directed design and synthesis of novel β (1-4)-glucosyltransferase (BGT) inhibitors. The designed inhibitors 1 5 provide conformational mimicry of the transition-state in glucosyltransfer reactions. The compounds were tested for i
Di-tert-butyl N,N-Diethylphosphoramidite. A New Phosphitylating Agent for the Efficient Phosphorylation of Alcohols
Perich, John W.,Johns, R. B.
, p. 142 - 144 (2007/10/02)
Alkyl and aryl di-tert-butyl phosphates were prepared in high yields by the 1H-tetrazole-promoted phosphitylation of alkyl and aryl alcohols with di-tert-butyl N,N-diethylphosphoramidite, followed by oxidation of the resultant alkyl and aryl di-tert-butyl
Synthesis of Alkyl Dihydrogenphosphate by the Reaction of Alcohols and Silyl Polyphosphate
Okamoto, Yoshiki
, p. 3393 - 3394 (2007/10/02)
Alkyl dihydrogenphosphates were readily prepared by phosphorylation of alcohols with trimethylsilyl polyphosphate of polyphosphorylated silica-gel.
Phosphorylation with Pyrophosphoric Acid
Yamaguchi, Hachiro,Ogura, Fumio,Otsubo, Tetsuo,Ikeura, Yasuhiro
, p. 1891 - 1892 (2007/10/02)
Dihydrogenphosphates of primary and secondary aliphatic alcohols as well as phenol were prepared by a very simple procedure with pyrophosphoric acid. t-Butyl and benzyl dihydrogenphosphates could be obtained by a slight modification of the reaction conditions.For the purpose of phosphorylation pyrophosphoric acid was more reactive than orthophosphoric acid.
