- Cleavage of phosphorus-carbon (P-C) bonds of α-amino phosphonates with intramolecular hydrogen migration in the gas phase using electrospray ionization tandem mass spectrometry
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RATIONALE α-Amino phosphonates with intrinsic biological activities have been used in a wide variety of applications. Because of the widespread existence of natural organophosphorus compounds containing P-C bonds such as the α-amino phosphonates, it is important to investigate the gas-phase chemistry of P-C bonds in order to determine their basic properties, which might provide some insights into their biosynthesis and catalytic cleavage. METHODS Twenty α-amino phosphonates were successfully synthesized and their fragmentation behavior was systematically investigated using in-solution deuterium labeling in combination with high-resolution Fourier transform ion cyclotron resonance (FTICR) electrospray ionization tandem mass spectrometry. RESULTS The fragmentation pathways of twenty α-amino phosphonates with different chemical structures were systematically studied. In general, P-C bonds could be easily cleaved via a novel intramolecular hydrogen atom migration from the amino group to the phosphoryl group through a five-membered-ring intermediate in the gas phase. A possible mechanism of the rearrangement of α-amino phosphonates is proposed. CONCLUSIONS An interesting intramolecular hydrogen atom migration between the amino and phosphoryl groups was observed with cleavage of the P-C bond in the molecule through a five-membered-ring intermediate. This characteristic fragmentation pathway not only provides some insights into the basic chemistry of compounds with P-C bonds, but could also have some applications in the structural determination of the α-amino phosphonate analogues. Copyright
- Gao, Yuzhen,Xu, Jian,He, Yaohui,Tang, Guo,Lin, Zhiwei,Liu, Hongxia,Gao, Xiang,Zhao, Yufen
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p. 1964 - 1970
(2014/08/18)
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- Direct transformation of amides into α-amino phosphonates via a reductive phosphination process
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The first general method for the reductive phosphination of amides in one pot has been developed. The reactions described provide a novel access to α-amino phosphonates in good to excellent yields, cover a broad scope of substrates such as secondary and tertiary amides, and do not require a low temperature.
- Gao, Yuzhen,Huang, Zhongbin,Zhuang, Rongqiang,Xu, Jian,Zhang, Pengbo,Tang, Guo,Zhao, Yufen
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supporting information
p. 4214 - 4217
(2013/09/12)
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- Phosphites mediated decarboxylation of α-iminoacids. A straightforward route to labelled α-aminophosphates
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Aminophosphates are of great interest owing to their biological activity. These products are considered as structural analogues of the corresponding aminoacids but also as transition state mimics of peptide hydrolysis. They are known to act as antibiotic and pharmacological agents as well as enzyme inhibitors. Despite the growing importance of these drugs, few methods have been reported for their labelling. These isotopic syntheses usually involve strong bases to generate an α-carbanion which is then quenched with D2O. In the present article we would like to report two novel procedures for the one pot synthesis of labelled α-aminophosphates. These procedures could easily be adapted to tritium labelling.
- Taran, Frederic,Doris, Eric,Noel, Jean-Pierre
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p. 287 - 295
(2007/10/03)
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- AN EFFICIENT SYNTHESIS OF 1-AMINOPHOSPHONIC ACIDS AND ESTERS BEARING HETEROCYCLIC MOIETY
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New α-aminophosphonic esters and acids derived from furan, thiophene and pyrazole were prepared in high yield, in the reactions of benzylamine, benzhydrylamine or benzyl carbamate with heterocyclic aldehydes and diethyl or diphenyl phosphonates.The protecting groups at amine (benzyl or benzhydryl) were removed by hydrogenolysis or hydrolysis, respectively.The N-benzoyloxycarbonyl (Z-group) was removed by treatment with 45percent HBr in acetic acid. Key words: Diphenyl α-aminofurylmethyl phosphonate, α-aminothienylmethylphosphonic acid, α-aminopyrazolylmethylphosphonic acid, imines, benzyl carbamate.
- Boduszek, Bogdan
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