Phase Transfer Assisted Permanganate Oxidations

Lee, Donald G.

doi:10.1016/b978-0-12-697253-5.50007-9

Cited by 32 publications

(5 citation statements)

References 66 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The cyclic manganese (V) ester intermediate is unstable and rapidly hydrolysed at both C-O-Mn bonds, more or less simultaneously to yield diols. [1][2][3] The yields of diols, however, are seldom above 50% though they can be improved with phase transfer catalysis [4][5][6] or by increased stirring. 7 The preparation and absorption spectrum of a stable solution of manganese (V) diesters by reacting alkenes with pulverised potassium permanganate in dichloromethane and benzyltriethylammonium chloride as a phase transfer agent has been reported 8,9 by Ogino and his group.…”

mentioning

confidence: 99%

Vicinal Dihydroxylation of Alkenes with Tetradecyltrimethylammonium permanganate and potassium hydroxide in a two phase Solvent System

Hazra

Pore

Chordia

et al. 2001

Journal of Chemical Research

View full text Add to dashboard Cite

show abstract

mentioning

confidence: 99%

Vicinal Dihydroxylation of Alkenes with Tetradecyltrimethylammonium permanganate and potassium hydroxide in a two phase Solvent System

Hazra

Pore

Chordia

et al. 2001

Journal of Chemical Research

View full text Add to dashboard Cite

show abstract

“…e osmium tetroxide catalytic oxidation of prochiral olefinic substrates together with asymmetric amine ligands as chiral auxiliaries shows a very high enantioface selectivity [6]. Experimental and theoretical works over the past year have shown the stability of epoxide formation via the catalyzed oxidation pathways by early transition metals such titanium, vanadium, and chromium [7][8][9] whereas oxo complexes such as ruthenium tetroxide [9], osmium tetroxide [4], and permanganate [10] tend to prefer cisdihydroxylate olefinic substrates [11]. Exploring and understanding the mechanistic channels of olefinic catalyzed substrates, especially osmium tetroxide, has been a subject of interest and study due to the relevance of their cis-dihydroxylate and epoxide products.…”

Section: Introductionmentioning

confidence: 99%

Quantum Mechanistic Studies of the Oxidation of Ethylene by Rhenium Oxo Complexes

Fosu

Obuah

Hamenu

et al. 2021

Journal of Chemistry

View full text Add to dashboard Cite

Transition-metal-mediated oxygen transfer reactions are of importance in both industry and academia; thus, a series of rhenium oxo complexes of the type ReO3L (L = O−, Cl−, F−, OH−, Br−, I−) and their effects as oxidation catalysts on ethylene have been studied. The activation and reaction energies for the addition pathways involving multiple spin states (singlet and triplet) have been computed. In all cases, structures on the singlet potential energy surfaces showed higher stability compared to their counterparts on the triplet potential energy surfaces (PESs). Frontier Molecular Orbital calculations show electrons flow from the HOMO of ethylene to the LUMO of rhenium for all complexes studied except ReO4− where the reverse case occurs. In the reaction between ReO3L (L = O−, Cl−, F−, OH−, Br−, and I−) and ethylene, the concerted [3 + 2] addition pathway on the singlet PES leading to the formation of dioxylate intermediate is favored over the [2 + 2] addition pathway leading to the formation of a metallaoxetane intermediate and subsequent rearrangement to the dioxylate. The activation and the reaction energies for the formation of the dioxylate on the singlet PES for the ligands studied followed the order O− > OH− > I− > F− > Br− > Cl− and O− > OH− > F− > I− > Br− > Cl−, respectively. Furthermore, the activation and the reaction energies for the formation of the metallaoxetane intermediate increase in the order O− > OH− > I− > Br− > Cl− > F− and O− > Br− > I− > Cl− > OH− > F−, respectively. The subsequent rearrangement of the metallaoxetane intermediate to the dioxylate is only feasible in the case of ReO4−. Of all the complexes studied, the best dioxylating catalyst is ReO3Cl (singlet surface) and the best epoxidation catalyst is ReO3F (singlet surface).

show abstract

“…They thought that an electron-withdrawing group such as fluorine on the alkene facilitates the nucleophilic attack by permanganate ions. Lee (1982) also pointed out that the oxidation of hydrocarbons could sometimes be facilitated by prior halogenation of the oxidation site. However, Freeman (1975) considered the permanganate ion as an electrophile in the reaction.…”

Section: Chemical Backgroundmentioning

confidence: 99%

Permanganate Treatment of DNAPLs in Reactive Barriers and Source Zone Flooding Schemes - Final Report

Schwartz¹

2000

View full text Add to dashboard Cite

Phase Transfer Assisted Permanganate Oxidations

Cited by 32 publications

References 66 publications

Vicinal Dihydroxylation of Alkenes with Tetradecyltrimethylammonium permanganate and potassium hydroxide in a two phase Solvent System

Vicinal Dihydroxylation of Alkenes with Tetradecyltrimethylammonium permanganate and potassium hydroxide in a two phase Solvent System

Quantum Mechanistic Studies of the Oxidation of Ethylene by Rhenium Oxo Complexes

Permanganate Treatment of DNAPLs in Reactive Barriers and Source Zone Flooding Schemes - Final Report

Contact Info

Product

Resources

About