91489-49-5Relevant academic research and scientific papers
Benzoyl methyl phosphates as efficient reagents in the one-pot tandem approach for the synthesis of 2-phenylbenzimidazoles in water
Hikawa, Hidemasa,Imani, Maki,Suzuki, Hideharu,Yokoyama, Yuusaku,Azumaya, Isao
, p. 3768 - 3773 (2014/01/06)
A novel and efficient method for the environmentally benign, catalyst- and auxiliary-free synthesis of 2-phenylbenzimidazoles in water is developed. Benzoyl methyl phosphates play important roles as biomimetic acylating agents for the one-pot tandem approach without additional catalysts.
Benzoyl methyl phosphate as an efficient reagent for the selective monobenzoylation of N-Bz-FTY720
Hikawa, Hidemasa,Hamada, Maiko,Yokoyama, Yuusaku,Azumaya, Isao
, p. 23131 - 23136 (2014/06/24)
A novel and efficient method for the selective monobenzoylation of N-Bz-FTY720 with benzoyl methyl phosphate (BMP) promoted by Zn(OAc)2 and Cs2CO3 was developed. Benzoyl methyl phosphate plays an important role as a biomimetic acylating agent for the monobenzoylation of 1,3-diols.
An efficient protocol for the amidation of carboxylic acids promoted by trimethyl phosphite and iodine
Luo, Qun-Li,Lv, Lina,Li, Yu,Tan, Jian-Ping,Nan, Wenhui,Hui, Qun
scheme or table, p. 6916 - 6922 (2012/01/06)
A practical, one-pot protocol is described for the conversion of carboxylic acids into amides through carboxyl activation by the reagent combination of trimethyl phosphite and iodine. This method integrates several advantages: (1) it allows amines to be chemoselectively acylated with excellent results in the presence of sulfur and oxygen nucleophiles; (2) the method shows wide generality in respect of solvent, base, and substrate; (3) the reagents used are widely available and much less expensive than common coupling reagents, and (4) the process is remarkably convenient, permitting extraction, recrystallization, and column chromatography as optional work-up procedures. The chemoselectivity and generality of the method, the low cost, and wide availability of reagents combined with the ease of use make it a very favorable process.
Activation of acyl phosphate monoesters by lanthanide ions: Enhanced reactivity of benzoyl methyl phosphate
Kluger, Ronald,Cameron, Lisa L.
, p. 3303 - 3308 (2007/10/03)
Acyl phosphate monoesters are intermediates in many biochemical acylation reactions, such as those involving aminoacyl adenylates. Benzoyl methyl phosphate, a typical acyl phosphate monoester, is slowly hydrolyzed in neutral solutions but reacts rapidly with amines. Since biochemical processes of acyl phosphate monoesters involve accelerated reactions with oxygen-centered nucleophiles, we sought catalysts for hydrolysis and methanolysis of benzoyl methyl phosphate to mimic the biochemical outcome. Lanthanide ions are particularly effective catalysts, accelerating reactions much more than comparable levels of magnesium ion. Detailed kinetic analysis of the hydrolysis reactions reveals formation of a 1:1 complex, followed by rapid reaction with a nucleophile. The hydroxide-dependent hydrolysis rate in the europium complex is about 105 times that of free substrate with hydroxide. A mechanism that accounts for the data and observed behavior involves bidentate coordination of the metal ion by the acyl phosphate through phosphate and carbonyl oxygens, lowering the energy of the tetrahedral addition intermediate and the associated transition states. The dependence of the metal ion catalyzed process on the concentration of hydroxide ion is consistent with coordinated hydroxide acting as a nucleophile. The reaction of benzoyl methyl phosphate with methanol to form methyl benzoate and methyl phosphate is 30 000 times more rapid in the presence of 0.0001 M lanthanum triflate (in the absence of the metal ion kobs = 2.1 × 10-7 s-1, at 25°C). Thus, the combination of acyl phosphate esters and lanthanide salts appears to be a promising method for biomimetic acylation of hydroxyl groups.
Preparation of esters and amides from carboxylic acids by activation with dialkyl phosphite-carbon tetrachloride mixture
Jaszay, Zsuzsa M.,Petnehazy, Imre,Toke, Laszlo
, p. 2761 - 2768 (2007/10/03)
A simple one pot phase transfer catalytic method is described for the synthesis of carboxylic amides and esters from carboxylic acids and amines or alcohols, respectively. For the activation of the carboxylic acids 'in situ' generated phosphoric acid diester chlorides were applied.
Photochemistry of Matrix-Isolated (α-Diazobenzyl)phosphonate. Observation and Reactions of Phosphonylphenylcarbene, Phosphonyl Phenyl Ketone Oxide, and Phenylphosphonyldioxirane
Tomioka, Hideo,Komatsu, Kazunori,Shimizu, Masayoshi
, p. 6216 - 6222 (2007/10/02)
Photolysis of dimethyl α-diazobenzylphosphonate (1) in an Ar matrix at 10 K resulted in the appearance of new absorption bands at 1268, 788, and 536 cm-1, attributable to the carbene 2.The assignment was based on the observation that the new ab
Phosphoryl to carbonyl migration of amino groups in mixed anhydrides
Symes, Jill,Modro, Tomasz A.
, p. 1702 - 1708 (2007/10/02)
Mixed anhydrides derived from carboxylic and aminophosphoric acids, (RO)(R'2N)P(O)OC(O)R'' (1), undergo unimolecular fragmentation yielding carboxyamides, R''C(O)NR'2, and metaphosphate esters, ROPO2.The mechanism of the amino group transfer was studied for substrate 1a (1, R = R' = Me; R'' = Ph); solvent as well as substituent effects indicate little (if any) charge development in the transition state.The effects of solvents and Lewis acids on the reaction rate and the activation parameters determined for 1a can be explained best in terms of stabilizing interactions with either carboxyamide or metaphosphate being formed in the course of reaction.The transfer of a functional group from one acyl center to another was investigated for other anhydride systems and the relative contributions of the fragmentation vs. disproportionation of substrates are discussed.
