Studies of the Interesting Gas‐phase Rearrangement Reactions of 2‐Pyrimidinyloxy‐<i>N</i>‐arylbenzylurea Promoted by Urea‐Carbamimidic Acid Tautomerism by ESI‐MS/MS and Theoretical Computation

Xu, Can; Wang, Haoyang; Zhao, Zhixiong; Tang, Qinghong; Guo, Yinlong; Lü, Long

doi:10.1002/cjoc.201090298

Cited by 4 publications

(4 citation statements)

References 28 publications

(40 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It is becoming increasingly recognized that the gas‐phase Smiles rearrangement is not confined to the classical five‐membered ring transition state. For example, both Wang and Pan proposed transition states of six‐membered rings, supported by theoretical calculations 24–28 . In addition, Pan's group highlighted that carbon monoxide (CO) could be eliminated through a three‐membered ring transition state 29 .…”

Section: Introductionmentioning

confidence: 94%

“…For example, both Wang and Pan proposed transition states of sixmembered rings, supported by theoretical calculations. [24][25][26][27][28] In addition, Pan's group highlighted that carbon monoxide (CO) could be eliminated through a three-membered ring transition state. 29 Concerning the extrusion of sulfur dioxide (SO 2 ), Lu and Irikura suggested that this process occurred through a five-membered ring transition state.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Gas‐phase Smiles rearrangement of ortho‐nitro‐substituted diaryliodonium cations and their mechanistic insights

Wei,

Pan,

Ling

et al. 2024

Rapid Comm Mass Spectrometry

View full text Add to dashboard Cite

RationaleDiaryliodonium salts are useful electrophilic reagents in organic chemistry, finding extensive applications in arylations and photo‐induced polymerizations. However, comprehensive mechanistic investigations, particularly concerning the mass spectrometric behaviors of diaryliodonium salts, are relatively scarce in the literature.MethodsDiaryliodonium salts could be readily ionized using electrospray ionization mass spectrometry (ESI‐MS) to give [Ar1‐I+‐Ar2], and high‐resolution ESI‐tandem mass spectrometry (MS/MS) experiments were conducted to investigate their gas‐phase chemical reactions.ResultsInvestigations on ESI‐MS/MS of [Ar1‐I+‐Ar2] revealed two major fragmentation patterns: (1) reductive elimination resulting in the diaryl coupling product ion [Ar1‐Ar2]+• by the loss of I; (2) generation of aryl cations [Ar1]+ or [Ar2]+ through cleavage of the C–I bonds. We revealed that the introduction of NO2 into Ar2 of [Ar1‐I+‐Ar2] could lead to an unexpected fragmentation ion [Ar1O]+ in MS/MS, arising from an O‐atom transfer process from NO2 to Ar1. Particularly, when NO2 was ortho‐positioned to the iodine in Ar2, the [Ar1O]+ sometimes exhibited dominant behavior.ConclusionsComprehensive ESI‐MS/MS studies and theoretical calculations provided strong support for the O‐atom transfer mechanistic pathway: [Ar1‐I+‐(o‐NO2‐Ar2)] initially underwent a Smiles rearrangement to the intermediate [Ar1‐O‐(o‐NO‐Ar2I)]+, which subsequently dissociated to [Ar1O]+ or [o‐NO‐Ar2I]+•. Herein, we proposed an unexpected “ortho effect” in the gas‐phase fragmentation reaction of [Ar1‐I+‐(o‐NO2‐Ar2)], in which the crucial determinant factor for the aryl migration was identified as the Smiles rearrangement reaction.

show abstract

Section: Introductionmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

Gas‐phase Smiles rearrangement of ortho‐nitro‐substituted diaryliodonium cations and their mechanistic insights

Wei,

Pan,

Ling

et al. 2024

Rapid Comm Mass Spectrometry

View full text Add to dashboard Cite

show abstract

“…For examples, both Wang and Pan proposed transition states of six-membered rings, supported by theoretical calculations. [24][25][26][27][28] Additionally, Pan's group highlighted that carbon monoxide (CO) could be eliminated through a three-membered ring transition state. 29 Concerning the extrusion of sulfur dioxide (SO 2 ), Lu and Irikura suggested that this process occurred through a five-membered ring transition state.…”

Section: Introductionmentioning

confidence: 99%

Gas-Phase Smiles Rearrangement of ortho-Nitro-substituted Diaryliodonium Cations and Their Mechanistic Insights

Wang,

Wei,

Pan

et al. 2023

Preprint

View full text Add to dashboard Cite

Rationale: Diaryliodonium salts are useful electrophilic reagents in organic chemistry, finding extensive applications in arylations and photo-induced polymerizations. However, the comprehensive mechanistic investigations, particularly concerning the mass spectrometric behaviors of diaryliodonium salts, are relatively scarce in the literatures. Methods: Diaryliodonium salts could be readily ionized in ESI-MS to give [Ar -I -Ar ], and the high-resolution ESI-MS/MS experiments were conducted to investigate their gas-phase chemical reactions. Results: Investigations on ESI-MS/MS of [Ar -I -Ar ] revealed two major fragmentation patterns: 1) Reductive elimination resulting the diaryl coupling product ion [Ar -Ar ] by the loss of I. 2) Generating aryl cations [Ar ] or [Ar ] through cleavage of the C–I bonds. We unrevealed that the introduction of NO into Ar of [Ar -I -Ar ] could lead to an unexpected fragmentation ion [Ar O] in MS/MS, arising from an O-atom transfer process from NO to Ar . Particularly, when NO was ortho-positioned to the iodine in Ar , the [Ar O] sometimes exhibited dominant behavior. Conclusions: Comprehensive ESI-MS/MS studies and theoretical calculations provided strong support for the O-atom transfer mechanistic pathway: [Ar -I -( o-NO -Ar )] initially underwent a Smiles rearrangement to the intermediate [Ar -O-( o-NO-Ar I)] , which subsequently dissociated to [Ar O] or [ o-NO-Ar I] . Herein, we proposed an unexpected ” ortho-effect” in the gas-phase fragmentation reaction of [Ar -I -( o-NO -Ar )], in which the crucial determinant factor for the aryl migration was identified as the Smiles rearrangement reaction.

show abstract

“…[23][24][25][26] Thus, the reactivity and structures of the reactive transient intermediates can then be further studied by MS/MS to provide clues for the study of reaction mechanisms. [27][28][29] The gas phase results of reaction system can reflect the system in liquid phase, [30,31] according to the gas phase results obtained by ESI-MS/MS, we can understand the process in the solution phase. Then we also synthesized the authentic Pd(IV) complex 3c•OAc and tried to ana-lyze it by ESI-MS/MS to further confirm the characteristic of the intercepted Pd(IV) transient intermediate in reaction solution.…”

Section: Introductionmentioning

confidence: 99%

Study of the Transient Reactive Pd(IV) Intermediate in the Pd(OAc)₂‐Catalyzed Oxidative Coupling Reaction System by Electrospray Ionization Tandem Mass Spectrometry

et al. 2013

Self Cite

View full text Add to dashboard Cite

Pd‐catalyzed oxidative coupling reaction was of great importance in the aromatic CH activation and the formation of new CO and CC bonds. Sanford has pioneered practical, directed CH activation reactions employing Pd(OAc)2 as catalyst since 2004. However, until now, the speculated reactive Pd(IV) transient intermediates in these reactions have not been isolated or directly detected from reaction solution. Electrospray ionization tandem mass spectrometry (ESI‐MS/MS) was used to intercept and characterize the reactive Pd(IV) transient intermediates in the solutions of Pd(OAc)2‐catalyzed oxidative coupling reactions. In this study, the Pd(IV) transient intermediates were detected from the solution of Pd(OAc)2‐catalyzed oxidative coupling reactions by ESI‐MS and the MS/MS of the intercepted Pd(IV) transient intermediate in reaction system was the same with the synthesized authentic Pd(IV) complex. Our ESI‐MS(/MS) studies confirmed the presence of Pd(IV) reaction transient intermediates. Most interestingly, the MS/MS of Pd(IV) transient intermediates showed the reductive elimination reactivity to Pd(II) complexes with new CO bond formation into product in gas phase, which was consistent with the proposed reactivity of the Pd(IV) transient intermediates in solution.

show abstract

Studies of the Interesting Gas‐phase Rearrangement Reactions of 2‐Pyrimidinyloxy‐N‐arylbenzylurea Promoted by Urea‐Carbamimidic Acid Tautomerism by ESI‐MS/MS and Theoretical Computation

Cited by 4 publications

References 28 publications

Gas‐phase Smiles rearrangement of ortho‐nitro‐substituted diaryliodonium cations and their mechanistic insights

Gas‐phase Smiles rearrangement of ortho‐nitro‐substituted diaryliodonium cations and their mechanistic insights

Gas-Phase Smiles Rearrangement of ortho-Nitro-substituted Diaryliodonium Cations and Their Mechanistic Insights

Study of the Transient Reactive Pd(IV) Intermediate in the Pd(OAc)₂‐Catalyzed Oxidative Coupling Reaction System by Electrospray Ionization Tandem Mass Spectrometry

Contact Info

Product

Resources

About

Studies of the Interesting Gas‐phase Rearrangement Reactions of 2‐Pyrimidinyloxy‐N‐arylbenzylurea Promoted by Urea‐Carbamimidic Acid Tautomerism by ESI‐MS/MS and Theoretical Computation

Cited by 4 publications

References 28 publications

Gas‐phase Smiles rearrangement of ortho‐nitro‐substituted diaryliodonium cations and their mechanistic insights

Gas‐phase Smiles rearrangement of ortho‐nitro‐substituted diaryliodonium cations and their mechanistic insights

Gas-Phase Smiles Rearrangement of ortho-Nitro-substituted Diaryliodonium Cations and Their Mechanistic Insights

Study of the Transient Reactive Pd(IV) Intermediate in the Pd(OAc)2‐Catalyzed Oxidative Coupling Reaction System by Electrospray Ionization Tandem Mass Spectrometry

Contact Info

Product

Resources

About

Study of the Transient Reactive Pd(IV) Intermediate in the Pd(OAc)₂‐Catalyzed Oxidative Coupling Reaction System by Electrospray Ionization Tandem Mass Spectrometry