Investigation of Coordination of Mg(II) Cations to 2-Pyrimidinyloxy- N -Arylbenzylamines by Electrospray Mass Spectrometry: Insights for Mg(II) Catalyzed Smiles Rearrangement Reactions
Restricted accessResearch articleFirst published online April, 2011
Investigation of Coordination of Mg(II) Cations to 2-Pyrimidinyloxy- N -Arylbenzylamines by Electrospray Mass Spectrometry: Insights for Mg(II) Catalyzed Smiles Rearrangement Reactions
The CH3OH solutions of pyrimidinyloxy-N-arylbenzylamines (1–5) in the presence of Mg(II)X2 salts (X = Cl or ClO4) were investigated by electrospray ionization mass spectrometry and tandem mass spectrometry (MS/MS) subsequently, showing that the cationic Mg(II) complexes1–5·MgX+ were important active complexes or intermediates for initiating interesting Smiles rearrangement reactions in both the gas- and solution phases. By using different MgX2 salts and selecting a set of reactants with different substitutes, the role of the counter-ion (X−) and the structure effect of the reactants on the Mg(II) catalyzed Smiles rearrangement reactions were studied. Moreover, the solvent effect on Mg(II) catalyzed Smiles rearrangement reactions was revealed by studying the CH3OH adduct complexes of1–5·MgCl+, which showed that the coordination of CH3OH to the Mg(II) center in the complexes decreased the reaction tendency. The mechanisms involved in the gas-phase Mg(II) catalyzed Smiles rearrangement reactions were proposed on the basis of MS/MS experiments and theoretical computations, showing some unique chemistries initiated by introducing Mg(II) into the template molecules.
McLuckeyS.A.GlishG.L.BuschK.L., Mass Spectrometry/Mass Spectrometry: Techniques and Applications of Tandem Mass Spectrometry.VCH Publishers Inc., New York, USA, p. 173 (1988).
2.
PorterC.J.BeynonJ.H.AstT., “The modern mass-spectrometer—a complete chemical laboratory”, Org. Mass Spectrom.16, 101 (1981). doi: 10.1002/oms.1210160302
3.
O'HairR.A.J., “The 3D quadrupole ion trap mass spectrometer as a complete chemical laboratory for fundamental gas-phase studies of metal mediated chemistry”, Chem. Commun.14, 1469 (2006). doi: 10.1039/b516348j
4.
GlishG.L.CooksR.G., “The Fischer Indole synthesis and pinacol rearrangement in the mass spectrometer”, J. Am. Chem. Soc.100, 6720 (1978). doi: 10.1021/ja00489a028
5.
TianZ.ChanB.SullivanM.B.RadomL.KassS.R., “Lithium monoxide anion: A ground-state triplet with the strongest base to date”, Proc. Natl. Acad. Sci. U. S. A.105, 7647 (2008). doi: 10.1073/pnas.0801393105
6.
EichingerP.C.H.DuaS.BowieJ.H., “Comparison of skeletal rearrangement reactions of even-electron anions in solution and in the gas phase”, Int. J. Mass Spectrom.133, 1 (1994). doi: 10.1016/0168-1176(94)03953-4
7.
CooksR.G.ChenH.EberlinM.N.ZhengX.TaoW.A., “Acetalization and transacetalization in the gas phase: The Eberlin reaction”, Chem. Rev.106, 188 (2006). doi: http://dx.doi.org/10.1016/0168-1176(94)03953-4
8.
SantosL.S.KnaackL.MetzgerJ.O., “Investigation of chemical reactions in solution using API-MS”, Int. J. Mass Spectrom.246, 84, (2005). doi: 10.1016/j.ijms2005.08.016
9.
SantosL.S., “Online mechanistic investigations of catalyzed reactions by electrospray ionization mass spectrometry: A tool to intercept transient species in solution”, Eur. J. Org. Chem.2, 235 (2008). doi: 10.1002/ejoc.200700723
10.
EberlinM.N., “Electrospray ionization mass spectrometry: A major tool to investigate reaction mechanisms in both solution and the gas phase”, Eur. J. Mass Spectrom.13, 19 (2007). doi: 10.1255/ejms.837
11.
Di MarcoV.B.BombiG.G., “Electrospray mass spectrometry (ESI-MS) in the study of metal–ligand solution equilibria”, Mass Spectrom. Rev.25, 347 (2006). doi: 10.1002/mas.20070
12.
MeyerM.M.KhairallahG.N.KassS.R.O'HairR.A.J., “Gas-phase synthesis and reactivity of the lithium acetate enolate anion ‘CH2CO2Li’”, Angew. Chem. Int. Ed.48, 2934 (2009). doi: 10.1002/anie.200900245
13.
TrageC.SchröderD.SchwarzH., “Coordination of iron (III) cations to β-keto esters as studied by electrospray mass spectrometry: Implications for iron-catalyzed Michael additions”, Chem. Eur. J.11, 618 (2005). doi: 10.1002/chem.200400715
14.
FürmeierS.Griep-RamingJ.HayenA.MetzgerJ.O., “Chelation-controlled radical chain reactions studied by electrospray ionization mass spectrometry”, Chem. Eur. J.11, 5545 (2005). doi: 10.1002/chem.200500188
15.
DucháčkováL.RoithováJ., “The interaction of zinc (II) and hydroxamic acids and a metal-triggered Lossen rearrangement”, Chem. Eur. J.15, 13399 (2009). doi: 10.1002/chem.200901645
16.
KadlčíkováA.ValterováI.DucháčkováL.RoithováJ.KotoraM., “Lewis base catalyzed enantioselective allylation of α,β-unsaturated aldehydes”, Chem. Eur. J.16, 9442 (2010). doi: 10.1002/chem.201001523
17.
SroglJ.HývlJ.RévészA.SchröderD., “Mechanistic insights into a copper-disulfide interaction in oxidation of imines by disulfides”, Chem. Commun.21, 3463 (2009). doi: 10.1039/b904403e
18.
WangH.Y.YimW.L.KlünerT.MetzgerJ.O., “ESI-MS studies and calculations on alkali metal adduct ions of ruthenium olefin metathesis catalysts and their catalytic activity in metathesis reactions”, Chem. Eur. J.15, 10948 (2009). doi: 10.1002/chem.200900565
19.
WangH.Y.GuoY.L.LuL., “Studies of rearrangement reactions of protonated and lithium cationized 2-pyrimidinyloxy-N-arylbenzylamine derivatives by MALDI-FT-ICR mass spectrometry”, J. Am. Soc. Mass Spectrom.15, 1820 (2004). doi: 10.1016/j.jasms.2004.08.014
WangH.Y.TangQ.H.ZhangX.GuoY.L.LuL., “Using tandem mass spectrometry to predict chemical transformations of 2-pyrimidinyloxy-N-arylbenzyl amine derivatives in solution”, J. Am. Soc. Mass Spectrom.17, 253 (2006). doi: 10.1016/j.jasms.2005.11.001
22.
XuC.WangH.Y.ZhuF.J.GuoY.L.LuL., “Studies of gas phase reactions of cationic iron complexes of 2-pyrimidinyloxy-N-arylbenzylamines by electrospray ionization tandem mass spectrometry”, Rapid Commun. Mass Spectrom.25, 169 (2011). doi: 10.1002/rcm.4848
23.
XiangJ.B.ZhengL.Y.XieH.X.HuaX.W.DangQ.BaiX., “Pyrrolo-dihydropteridines via a Cascade reaction consisting of iminium cyclization and O–N Smiles rearrangement”, Tetrahedron64, 9101 (2008). doi: 10.1016/j.tet.2008.07.002
24.
StaceA.J., “Metal ion solvation in the gas phase: The quest for higher oxidation states”, J. Phys. Chem. A.35, 7993 (2002). doi: 10.1021/jp020694t
25.
O'HairR.A.J., “Formation, chemistry and structure of organomagnesium species in solvent-free environments”, in The Chemistry of Organomagnesium Compounds, Ed by RappoportZ.MarekI., John Wiley & Sons Ltd, Chichester, UK, p. 155 (2008).
26.
O'HairR.A.J.VrkicA.K.JamesP.F., “Gas phase synthesis and reactivity of the organomagnesates [CH3MgL2]− (L=Cl and =O2CCH3): From ligand effects to catalysis”, J. Am. Chem. Soc.126, 12173 (2004). doi: 10.1021/ja048476w
27.
KhairallahG.N.O'HairR.A.J., “Dehydrogenation of formic acid catalyzed by magnesium hydride anions HMgL2− (L=Cl and HCO2)”, Int. J. Mass Spectrom.254, 145 (2006). doi: 10.1016/j.ijms.2006.04.011
28.
JacobA.P.JamesP.F.O'HairR.A.J., “Do alkali and alkaline earth acetates form organometallates via decarboxylation? A survey using electrospray ionization tandem mass spectrometry and DFT calculations”, Int. J. Mass Spectrom.255–256, 45 (2006). doi: 10.1016/j.ijms.2005.08.015
29.
JamesP.F.PeruginiM.A.O'HairR.A.J., “Collision induced dissociation of [metal(L)2]2+ complexes (metal=Cu, Ca and Mg) of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine allows distinction of the acyl groups at the sn1 and SN2 positions”, Eur. J. Mass Spectrom.13, 433 (2007). doi: 10.1255/ejms.897
30.
ThumC.C.L.KhairallahG.N.O'HairR.A.J., “Gas-phase formation of the Gomberg–Bachmann magnesium ketyl”, Angew. Chem. Int. Ed.47, 9118 (2008). doi: 10.1002/anie.200803463
31.
KhairallahG.N.ThumC.C.L.O'HairR.A.J., “A second metal center enhances the reactivity of an organomagnesate: Comparison of the gas-phase reactions of water with [RCCMgCl2]− and [RCCMg2Cl4]− (R=H, Ph)”, Organometallics28, 5002 (2009). doi: 10.1021/om900426h
32.
KhairallahG.N.YooE.J.H.O'HairR.A.J., “Formation of methylmagnesium or coordinated ylide? Competition between decarboxylation of acetate and betaine ligands in [CH3CO2MgO2CCH2X (CH3)2]+ (where X=NCH3 and S)”, Organometallics29, 1238 (2010). doi: 10.1021/om901050s
33.
SchröderD.RoithováJ., “Low-temperature activation of methane: It also works without a transition metal”, Angew.Chem. Int. Ed.45, 5705 (2006). doi: 10.1002/anie.200601273
34.
Jagoda-CwiklikB.JungwirthP.RulišekL.MilkoP.RoithováJ.LemaireJ.MaitreP.OrtegaJ.M.SchröderD., “Micro-hydration of the MgNO3+ cation in the gas phase”, ChemPhysChem.8, 1629 (2007). doi: 10.1002/cphc.200700196
35.
SchröderD.RoithováJ.AlikhaniE.KwapienK.SauerJ., “Preferential activation of primary C–H bonds in the reactions of small alkanes with the diatomic MgO+• cation”, Chem. Eur. J.16, 4110 (2010). doi: 10.1002/chem.200902373
36.
FürmeierS.MetzgerJ.O., “Detection of transient radical cations in electron transfer initiated Diels–Alder reactions by electrospray ionization mass spectrometry”, J. Am. Chem. Soc.126, 14485 (2004). doi: 10.1021/ja046157z
37.
MarquezC.MetzgerJ.O., “ESI-MS study on the aldol reaction catalyzed by l-proline”, Chem. Commun.14, 1539 (2006). doi: 10.1039/b518288c
38.
WangH.Y.MetzgerJ.O., “ESI-MS study on first generation ruthenium olefin metathesis catalysts in solution: Direct detection of the catalytically active 14-electron ruthenium intermediate”, Organometallics27, 2761 (2008). doi: 10.1021/om800003r
39.
MarquezC.A.WangH.Y.FabbrettiF.MetzgerJ.O., “Electron-transfer-catalyzed dimerization of trans-anethole: Detection of the distonic tetramethylene radical cation intermediate by extractive electrospray ionization mass spectrometry”, J. Am. Chem. Soc.130, 17208 (2008). doi: 10.1021/ja806791c
PC Spartan Pro, version 1.0.7. Wavefunction Inc., Irvine, CA, USA (2001).
42.
WalkerN.DobsonM.P.WrightR.R.BarranP.E.MurrellJ.N.StaceA.J., “A gas-phase study of the co ordination of Mg2+ with oxygen- and nitrogen-containing ligands”, J. Am. Chem. Soc.122, 11138 (2000). doi: 10.1021/ja0007509
43.
EichingerP.C.H.BowieJ.H.HayesR.H., “The gas-phase Smiles rearrangement: A heavy atom labeling study”, J. Am. Chem. Soc.111, 4224 (1989). doi: 10.1021/ja00194a011
44.
EichingerP.C.H.BowieJ.H., “The gas-phase Smiles rearrangement. The effect of ring substitution. An oxygen-18 labeling study”, Org. Mass Spectrom.27, 995 (1992). doi: 10.1002/oms.1210271007
45.
ChenH.ChenH.W.CooksR.G., “Complexes bonded at carbon and at oxygen”, J. Am. Soc. Mass Spectrom.15, 998 (2004). doi: 10.1016/j.jasms.2004.03.006
46.
WangF., “Collision-induced gas-phase Smiles rearrangement in phenoxy-N-phenyl-acetamide derivatives”, Rapid. Commun. Mass Spectrom.20, 1820 (2006). doi: 10.1002/rcm.2492
47.
ZhouY.P.PanY.J.CaoX.J.WuJ.JiangK.Z., “Gas-phase Smiles rearrangement reactions of deprotonated 2-(4,6-dimethoxypyrimidin-2-yisulfanyl)-N-phenyl benzamide and its derivatives in electrospray ionization mass spectrometry”, J. Am. Soc. Mass Spectrom.18, 1813 (2007). doi: 10.1016/j.jasms.2007.07.012
48.
HeM.McLuckeyS.A., “Tandem mass spectrometry of half-generation PAMAM dendrimer anions”, Rapid Commun. Mass Spectrom.18, 960 (2004). doi: 10.1002/rcm.1431
49.
ShenL.ShaY.W.HongX.Y., “Tandem mass spectrometric analysis of distinct fragmentation patterns to [M+Na]/Z and [M+H]/Z of dendritic Al (III) and Zn (II) quinolates”, Rapid Commun. Mass Spectrom.18, 1534 (2004). doi: 10.1002/rcm.1517
50.
WangH.Y.ZhangX.GuoY.L.LuL., “Mass spectrometric studies of the gas phase retro-Michael type fragmentation reactions of 2-hydroxybenzyl-N-pyrimidinyl amine derivatives”, J. Am. Soc. Mass Spectrom.16, 1561 (2005). doi: 10.1016/j.jasms.2005.05.006
51.
TruceW.E.KreiderE.M.BrandW.W., “The Smiles and related rearrangements of aromatic systems”, in Organic Reactions, Vol. 18. John Wiley & Sons Inc., New York, USA, p. 99 (1970).
52.
RádlS., “Aromatic nucleophilic denitrocyclization reactions”, in Advances in Heterocyclic Chemistry, Vol. 83. Academic Press, San Diego, CA, USA, p. 189 (2002).
