Competitive McLafferty-type rearrangements of sodium adduct of anti- 2,3-dihydroxy-1-phenylpentane-1,4-dione compounds in tandem mass spectrometry

Abstract

Sodium adducts of anti-2,3-dihydroxy-1-phenylpentane-1,4-dione compounds with different substituents were studied by collision-induced dissociation. McLafferty-type rearrangements preceding fragmentation were found as their main fragmentation pathway. Coordination of sodium cation to the oxygen functions may either lead to formation of a five-membered or a six-membered ring. Two McLafferty-type rearrangement product ions exhibiting a mass difference of 2 u indicated that two competitive McLafferty-type rearrangements through a six-membered ring coordination occurred. Relative abundances of the corresponding product ions were studied by energy-resolved collision-induced dissociation experiments and density functional theory calculations. Furthermore, the influence of different substituents was probed.

Keywords

McLafferty-type rearrangement sodium adduct six-membered ring coordination energy-resolved collision-induced dissociation DFT calculation

Get full access to this article

View all access options for this article.

References

McLafferty

. Mass spectrometric analysis: broad applicability to chemical research. Anal Chem 1956; 28: 306.

Gilpin

McLafferty

. Mass spectrometric analysis: aliphatic aldehydes. Anal Chem 1957; 29: 990.

McLafferty

. Mass spectrometric analysis: molecular rearrangements. Anal Chem 1959; 31: 82.

Gross

. Focus in honor of Fred McLafferty, 2003 distinguished contribution awardee, for the discovery of the “McLafferty Rearrangement”. J Am Soc Mass Spectrom 2004; 15: 951.

Cai

Xie

et al.

Fragmentation study of limonoids from Turraae pubescens by electrospray ionization quadrupole time-of-flight mass spectrometry. Anal Lett 2017; 50: 2908.

Demarque

Crotti

Vessecchi

et al.

Fragmentation reactions using electrospray ionization mass spectrometry: an important tool for the structural elucidation and characterization of synthetic and natural products. Nat Prod Rep 2016; 33: 432.

Cai

Guo

et al.

Recent (2000–2015) developments in the analysis of minor unknown natural products based on characteristic fragment information using LC–MS. Mass Spectrom Rev 2018; 37: 202.

Evans

Welch

Speed

AWH

et al.

An aldol-based synthesis of (+)-peloruside a, a potent microtubule stabilizing agent. J Am Chem Soc 2009; 131: 3840.

Zhang

Yang

et al.

Enantioselective direct synthesis of syn-and anti-α, β-dihydroxy γ-keto esters using a dinuclear zinc–AzePhenol complex. Eur J Org Chem 2018; 6: 785.

10.

Morisaki

Inoue

Kobayashi

et al.

Coordination of alkali metal cation to oxygen functions to form adduct ion in fast atom bombardment mass spectrometry. Tetrahedron 1996; 52: 9017.

11.

Andrey O. Process for the preparation of 1, 4-dialkyl-2, 3-diol-1, 4-butanedione. US Patent 8,129,570. 2012-3-6.

12.

Becke

. A new mixing of Hartree–Fock and local density-functional theories. J Chem Phys 1993; 98: 1372.

13.

Lee

Yang

Parr

. Development of the Colle–Salvetti correlation energy formula into a functional of the electron density. Phys Rev B: Condens Matter 1988; 37: 785.

14.

Ditchfield

Hehre

Pople

. Self-consistent molecular-orbital methods. IX. An extended Gaussian-type basis for molecular-orbital studies of organic molecules. J Chem Phys 1971; 54: 724.

15.

Heher

Ditchfield

Pople

. Self-consistent molecular-orbital methods. XII. Further extensions of Gaussian-type basis sets for use in molecular orbital studies of organic molecules. J Chem Phys 1972; 56: 2257.

16.

Hariharan

Pople

. The influence of polarization functions on molecular orbital hydrogenation energies. Theor Chim Acta 1973; 28: 213.

17.

Frisch MJ, Trucks GW, Schlegel HB, et.al. Gaussian 09, Revision D.01. Wallingford: Gaussian, Inc., 2009.

18.

Gonzalez

Schlegel

. An improved algorithm for reaction path following. J Chem Phys 1989; 90: 2154.

19.

Chai

Pan

. The effect of cation size (H⁺, Li⁺, Na⁺, and K⁺) on McLafferty-type rearrangement of even-electron ions in mass spectrometry. Sci China Chem 2014; 57: 662.

20.

Schulz

Jasikova

Skriba

et al.

Role of gold (I) α-oxo carbenes in the oxidation reactions of alkynes catalyzed by gold (I) complexes. J Am Chem Soc 2014; 136: 11513.

21.

Sun

Jin

Quan

et al.

Gas phase chemistry of N-benzylbenzamides with silver (I) cations: characterization of benzylsilver cation. Org Biomol Chem 2015; 13: 2561.

Supplementary Material

Please find the following supplemental material available below.

For Open Access articles published under a Creative Commons License, all supplemental material carries the same license as the article it is associated with.

For non-Open Access articles published, all supplemental material carries a non-exclusive license, and permission requests for re-use of supplemental material or any part of supplemental material shall be sent directly to the copyright owner as specified in the copyright notice associated with the article.

0.00 MB

0.25 MB