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. (30th September 2014)

• Record Type: Journal Article
• Authors: Gao, Yuzhen; Xu, Jian; He, Yaohui; Tang, Guo; Lin, Zhiwei; Liu, Hongxia; Gao, Xiang; Zhao, Yufen
• Is Part Of: Rapid communications in mass spectrometry. Volume 28:Number 18(2014)
• Page Start: 1964
• Page End: 1970
• Publication Date: 2014-09-30
• Subjects: Mass spectrometry -- Periodicals; 543.65
• DOI: 10.1002/rcm.6984
• Languages: English
• ISSNs: 0951-4198

Abstract

<abstract abstract-type="main"> <title> <x xml:space="preserve">Abstract</x> </title> <sec id="rcm6984-sec-0001" sec-type="section"> <title>RATIONALE</title> <p>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.</p> </sec> <sec id="rcm6984-sec-0002" sec-type="section"> <title>METHODS</title> <p>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.</p> </sec> <sec id="rcm6984-sec-0003" sec-type="section"> <title>RESULTS</title> <p>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.</p> </sec> <sec id="rcm6984-sec-0004" sec-type="section"> <title>CONCLUSIONS</title> <p>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 © 2014 John Wiley & Sons, Ltd.</p> </sec> </abstract>