期刊
JOURNAL OF MASS SPECTROMETRY
卷 48, 期 4, 页码 423-429出版社
WILEY
DOI: 10.1002/jms.3162
关键词
benzyl cation transfer; hydride transfer; activation of the amino hydrogen; the substituent effect; INC
资金
- National Science Foundation of China [21205025]
- National Science Foundation of Zhejiang Province [Y4100020]
In this study, the gas phase chemistry of the protonated benzyl esters of proline has been investigated by electrospray ionization mass spectrometry and theoretical calculation. Upon collisional activation, the protonated molecules undergo fragmentation reactions via three primary channels: (1) direct decomposition to the benzyl cation (m/z 91), (2) formation of an ion-neutral complex of [benzyl cation+proline]+, followed by a hydride transfer to generate the protonated 4,5-dihydro-3H-pyrrole-2-carboxylic acid (m/z 114), and (3) electrophilic attack at the amino by the transferring benzyl cation, and the subsequent migration of the activated amino proton leading to the simultaneous loss of (H2O+CO). Interestingly, no hydrogen/deuterium exchange for the fragment ion m/z 114 occurs in the d-labeling experiments, indicating that the transferring hydride in path-b comes from the methenyl hydrogen rather than the amino hydrogen. For para-substituted benzyl esters, the presence of electron-donating substituents significantly promotes the direct decomposition (path-a), whereas the presence of electron-withdrawing ones distinctively inhibits that channel. For the competing channels of path-b and path-c, the presence of electron-donating substituents favors path-b rather than path-c, whereas the presence of electron-withdrawing ones favors path-c rather than path-b. Copyright (c) 2013 John Wiley & Sons, Ltd.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据