Fragmentation of pentacoordinate spirobicyclic aminoacyl-phosphoranes (P-AAs) by electrospray ionization tandem mass spectrometry concerning P–O and P–N bond cleavage

Authors

  • Xiaomei Hu,

    1. Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, P.R. China
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  • Xiang Gao,

    1. Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, P.R. China
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  • Jun Zhu,

    Corresponding author
    • Department of Chemistry and Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, P.R. China
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  • Zhiping Zeng,

    1. Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, P.R. China
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  • Xinghua Zhang,

    1. Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, P.R. China
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  • Zhiwei Lin,

    1. Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, P.R. China
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  • Pengxiang Xu,

    Corresponding author
    • Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, P.R. China
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  • Yan Liu,

    1. Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, P.R. China
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  • Yufen Zhao

    1. Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, P.R. China
    2. The Key Laboratory for Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, School of Sciences, Tsinghua University, Beijing, P.R. China
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J. Zhu or P. X. Xu, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P.R. China.

E-mail: jun.zhu@xmu.edu.cn; xpengxiang@xmu.edu.cn

Abstract

The fragmentation pathways of both protonated and sodiated pentacoordinate spirobicyclic aminoacylphosphoranes (P-AAs) have been studied by electrospray ionization multi-stage mass spectrometry (ESI-MSn) in positive mode. The possible pathways and their mechanisms are elucidated through the combination of ESI-MS/MS, isotope (15 N and 2H) labeling and high-resolution Fourier transform ion cyclotron resonance (FTICR)-MS/MS. The relative Gibbs free energies (ΔG) of the product ions and possible fragmentation pathways are estimated at the B3LYP/6-31 G(d) level of theory. The theoretical calculations show that both protonated and sodiated P-AAs would quickly fragment before Berry pseudorotation. For protonated P-AAs, they have different tendencies to P–O or P–N bond cleavage. For sodiated P-AAs, the P–N bond is easier to cleave and produces the tetracoordinated phosphorus ion H. These results to some extent may give a clue to the chemistry of the active sites of phosphoryl transfer enzymes and will enrich the gas-phase ESI-MS ion chemistry of pentacoordinate phosphoranes. Copyright © 2011 John Wiley & Sons, Ltd.

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