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Oxygen Atom Transfer in the Oxidation of Dimethyl Sulfoxide by Oxoammonium Cations
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2021-01-15 , DOI: 10.1021/acs.joc.0c02526 Vasily D. Sen’ 1 , Valery A. Golubev 1 , Gennadii V. Shilov 1 , Alexander V. Chernyak 1 , Vladimir A. Kurmaz 1 , Victor B. Luzhkov 1, 2
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2021-01-15 , DOI: 10.1021/acs.joc.0c02526 Vasily D. Sen’ 1 , Valery A. Golubev 1 , Gennadii V. Shilov 1 , Alexander V. Chernyak 1 , Vladimir A. Kurmaz 1 , Victor B. Luzhkov 1, 2
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Cyclic oxoammonium salts and DMSO are known as important reagents for their diverse and unique reactivity. In the present work, we have studied the reaction of six- and five-membered oxoammonium salts with DMSO. The reaction includes ∼100% selective transfer of the O atom from the >N+═O group to the S atom of DMSO and structural rearrangement of the remaining cationic framework, leading to the formation of hydrolytically unstable iminium salts. The logarithms of the bimolecular rate constants k of the reaction correlated linearly with the reduction potentials E>N+═O/>N—O•, a relationship known for other electrophile–nucleophile combinations. The kinetic data and results of the DFT calculations allow for the suggestion that the studied process proceeds via the prereactive charge-transfer complex >N+═O···S (O)Me2 and its direct concerted rearrangement to the iminium salts. An alternative mechanism that includes intermediate steps with discrete nitrenium cations can be ruled out on the basis of product analysis and DFT computations. The obtained results allow a deeper understanding of the redox chemistry of a pair of nitroxide radicals-oxoammonium cations.
中文翻译：
氧铵阳离子氧化二甲亚砜中的氧原子转移
环状氧铵盐和DMSO因其多样而独特的反应性而被认为是重要的试剂。在目前的工作中，我们研究了六元和五元氧铵盐与DMSO的反应。反应包括〜100％的O原子从> N + = O基团选择性转移至DMSO的S原子，以及其余阳离子骨架的结构重排，导致形成水解不稳定的亚胺盐。反应的双分子速率常数k的对数与还原电位E > N + ═O/> N-O •线性相关，这种关系以其他亲电试剂-亲核试剂组合而闻名。动力学数据和DFT计算的结果表明，所研究的过程是通过> N + ═O··S（O）Me 2预反应电荷转移络合物进行的，并且其直接协同重排成亚胺盐。基于产物分析和DFT计算，可以排除包括具有离散的氮阳离子的中间步骤的替代机制。所获得的结果可以使人们更深入地了解一对氮氧化物自由基-氧铵盐阳离子的氧化还原化学。
更新日期：2021-02-19
中文翻译：
氧铵阳离子氧化二甲亚砜中的氧原子转移
环状氧铵盐和DMSO因其多样而独特的反应性而被认为是重要的试剂。在目前的工作中，我们研究了六元和五元氧铵盐与DMSO的反应。反应包括〜100％的O原子从> N + = O基团选择性转移至DMSO的S原子，以及其余阳离子骨架的结构重排，导致形成水解不稳定的亚胺盐。反应的双分子速率常数k的对数与还原电位E > N + ═O/> N-O •线性相关，这种关系以其他亲电试剂-亲核试剂组合而闻名。动力学数据和DFT计算的结果表明，所研究的过程是通过> N + ═O··S（O）Me 2预反应电荷转移络合物进行的，并且其直接协同重排成亚胺盐。基于产物分析和DFT计算，可以排除包括具有离散的氮阳离子的中间步骤的替代机制。所获得的结果可以使人们更深入地了解一对氮氧化物自由基-氧铵盐阳离子的氧化还原化学。
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