3614-36-6Relevant academic research and scientific papers
Evaluation of Natural and Synthetic Phosphate Donors for the Improved Enzymatic Synthesis of Phosphate Monoesters
Tasnádi, Gábor,Jud, Wolfgang,Hall, Mélanie,Baldenius, Kai,Ditrich, Klaus,Faber, Kurt
supporting information, p. 2394 - 2401 (2018/05/14)
Undesired product hydrolysis along with large amounts of waste in form of inorganic monophosphate by-product are the main obstacles associated with the use of pyrophosphate in the phosphatase-catalyzed synthesis of phosphate monoesters on large scale. In order to overcome both limitations, we screened a broad range of natural and synthetic organic phosphate donors with several enzymes on a broad variety of hydroxyl-compounds. Among them, acetyl phosphate delivered stable product levels and high phospho-transfer efficiency at the lower functional pH-limit, which translated into excellent productivity. The protocol is generally applicable to acid phosphatases and compatible with a range of diverse substrates. Preparative-scale transformations using acetyl phosphate synthesized from cheap starting materials yielded multiple grams of various sugar phosphates with up to 433 g L?1 h?1 space-time yield and 75% reduction of barium phosphate waste. (Figure presented.).
Toward a clean alternative to Friedel-Crafts acylation: In situ formation, observation, and reaction of an acyl bis(trifluoroacetyl)phosphate and related structures
Smyth, Timothy P.,Corby, Brian W.
, p. 8946 - 8951 (2007/10/03)
Reaction of acyl trifluoroacetates with phosphoric acid in the presence of trifluoroacetic anhydride (TFAA) leads to the ready formation of acyl bis(trifluoroacetyl)phosphates, which are powerful acylating agents. Formation of these species and the subsequent acylation reaction are carried out, without added solvent, in a single in situ reaction process. In this reaction system, anisole is rapidly acylated at ambient temperature using a variety of carboxylic acids giving the para isomer exclusively. TFAA acts as an activating agent and can be recovered from the reaction system as trifluoroacetic acid (TFA) and converted back to TFAA using a dehydrating agent, while phosphoric acid behaves as a covalent catalyst in the process. This reaction system has many features which are required elements of a clean alternative to the Friedel-Crafts process.
Nucleophilic Reactivity toward Acetyl Chloride in Water
Palling, David J.,Jencks, William P.
, p. 4869 - 4876 (2007/10/02)
Rate constant ratios for the reactions of acetyl chloride with nucleophilic reagents in water containing 2.5percent (v/v) dioxane were determined by product analysis.The rate constants show a small dependence on the basicity of primary amines, with βnuc=0.25, and are assigned to rate-limiting attack of the nucleophile.Pyridines with pKa>5 behave similarly, with βnuc=0.24, but less basic pyridines react more slowly.Several "α-effect" amines and anionic oxygen nucleophiles show small rate enhancements that are attributed to increases in the rate of nucleophilic attack.The rate constants do not fit the N+ correlation equation, and it is concluded that the reactions of nucleophilic reagents with acyl compounds are not satisfactorily correlated by simple modifications of this equation.
