Study on the reactive transient α‐λ³‐iodanyl‐acetophenone complex in the iodine(III)/PhI(I) catalytic cycle of iodobenzene‐catalyzed α‐acetoxylation reaction of acetophenone by electrospray ionization tandem mass spectrometry

Abstract

These ESI-MS/MS studies showed the existence of the reactive α-λ(3)-iodine alkyl acetophenone intermediate 3 in the catalytic cycle. Moreover, the gas-phase reactivity of 3·H(+) was consistent with the proposed solution-phase reactivity of the α-λ(3)-iodine alkyl acetophenone intermediate 3, thus confirming the reaction mechanism proposed by Ochiai.

Hypervalent Iodine‐Catalyzed Oxidative Functionalizations Including Stereoselective Reactions

“…On subsequent S N 2 displacement, the intermediate provides α‐functionalized ketones 2 , 109 or 115 with regeneration of iodobenzene. In addition, the presented mechanism was also supported by ESI‐MS experiments 60b…”

Iodine‐Catalyzed Oxidative Coupling Reactions Utilizing CH and XH as Nucleophiles

“…[42] Notably, ad etailed mechanistic study of this reaction was reported by Wang andc o-workersi n2 012, in whiche lectrospray ionization tandem mass spectrometry (ESI-MS/MS) was utilized as an efficient monitoring toolt oc learly revealt he generation of hypervalent iodine species. [43] In addition to acetic acids, sulfonica cids have also been employed in the a-tosyloxylation of ketones catalyzed by iodine.…”

“…As eries of different substituted isoquinolones could be synthesized in good yields at room temperature within 1h [Eq. (43)]. T he reaction was believed to be initiated by NÀIb ond formation between the substrate and in situ generated PhI(OAc) 2 .S ubsequentd isproportionation of the NÀIbondedi ntermediate gave an itrogen cation and regenerated PhI.…”

Gas Phase Decarbonylation and Cyclization Reactions of Protonated N-Methyl-N-Phenylmethacrylamide and Its Derivatives Via an Amide Claisen Rearrangement

“…Certain analogies between reaction mechanisms in the gas phase and solution have been known for a long time [1][2][3][4][5][6][7][8][9][10]19]. The reactivities and behaviors of ionic species in the gas phase and in solution can be correlated [12,[20][21][22], and there is a significant association between gas phase reactions and the analogous reactions in solution. Tandem mass spectrometry does not require large quantities of organic solvents and chemicals, and could be used as a high-throughput and green method to predict the chemical transformations of reactive compounds in solution.…”