- Twist does a twist to the reactivity: Stoichiometric and catalytic oxidations with twisted tetramethyl-IBX
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The methyl groups in TetMe-IBX lower the activation energy corresponding to the rate-determining hypervalent twisting (theoretical calculations), and the steric relay between successive methyl groups twists the structure, which manifests in significant solubility in common organic solvents. Consequently, oxidations of alcohols and sulfides occur at room temperature in common organic solvents. In situ generation of the reactive TetMe-IBX from its precursor iodo-acid, i.e., 3,4,5,6-tetramethyl-2-iodobenzoic acid, in the presence of oxone as a co-oxidant facilitates the oxidation of diverse alcohols at room temperature.
- Moorthy, Jarugu Narasimha,Senapati, Kalyan,Parida, Keshaba Nanda,Jhulki, Samik,Sooraj, Kunnikuruvan,Nair, Nisanth N.
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experimental part
p. 9593 - 9601
(2012/01/03)
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- Acetyl Exchange between Acetyl Chloride and Sterically Hindered Aryl Ketones under Friedel-Crafts Condition
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The kinetics of acetyl exchange between acetylmesitylene, or acetyldurene, and (14)C-labelled acetyl chloride have been measured in nitromethane solution in the presence of aluminium chloride.Mechanistic studies using acetylmesitylene as substrate show conclusively that acetyl exchange proceeds, not by acylation-deacylation or deacylation-acylation, but via a synchronous reaction involving an ipso-complex.Theoretical calculations (MNDO) indicate that of three possible synchronous pathways, two are energitically feasible.
- Andreou, Andreas D.,Bulbulian, Roger V.,Gore, Peter H.,Morris, Donald F. C.,Short, Eric L.
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p. 830 - 837
(2007/10/02)
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