Oxidative Cleavage of Olefins by In Situ-Generated Catalytic 3,4,5,6-Tetramethyl-2-iodoxybenzoic Acid/Oxone

Abstract

Oxidative cleavage of a variety of olefins to the corresponding ketones/carboxylic acids is shown to occur in a facile manner with 3,4,5,6-tetramethyl-2-iodobenzoic acid (TetMe-IA)/oxone. The simple methodology involves mere stirring of the olefin and catalytic amount (10 mol %) of TetMe-IA and oxone in acetonitrile-water mixture (1:1, v/v) at rt. The reaction mechanism involves initial dihydroxylation of the olefin with oxone, oxidative cleavage by the in situ-generated 3,4,5,6-tetramethyl-2-iodoxybenzoic acid (TetMe-IBX), and oxidation of the aldehyde functionality to the corresponding acid with oxone. Differences in the reactivities of electron-rich and electron-poor double bonds have been exploited to demonstrate chemoselective oxidative cleavage in substrates containing two double bonds.

Micellar Catalysis for Sustainable Hydroformylation

“…13 C NMR (151 MHz, CD 3 OD) δ 161.6, 131.2, 128.2, 127.7 (2 C), 127.2, 113.9, 69.7. The spectral data were identical to those reported in the literature [60] …”

Oxidative cleavage of C–C double bond in cinnamic acids with hydrogen peroxide catalysed by vanadium(v) oxide

“…Alternatively, many other oxidants have been investigated to achieve selective oxidative cleavage of double bonds, e.g. OsO 4 /NaIO 4 (Lemieux-Johnson reaction) 8,9 , Oxone 10,11 , m-CPBA 12 , t-BuOOH [13][14][15] , KMnO 4 16,17 … These methods also have some disadvantages, such as toxicity, high price, and generation of stoichiometric oxidant as waste. Using biobased molecules as feedstock demands the use of environmentally friendly oxidants such as oxygen and hydrogen peroxide.…”

Recent Advances in Transition‐Metal‐Free Oxygenation of Alkene C=C Double Bonds for Carbonyl Generation

“…The reaction was proposed to be catalyzed by the in situ‐generated hydroxyl‐(4‐carboxyphenyl)iodonium ion additive through the oxidation of ozone to the iodobenzoic acid, and intermediates 18 and 19 were possible key intermediates during the formation of the carboxylic acid products (Scheme ). Interestingly, recent work by Moorthy and Parida disclosed that similar oxygenation could also be realized by means of the in situ‐generated hypervalent iodine catalyst by employing o ‐iodobenzoic acid and ozone . As outlined in Scheme , the presence of ozone and 3,4,5,6‐tetramethyl‐2‐iodobenzoic acid (TetMe‐IA) enabled the oxygenation of alkenes 16 to provide carbonyl products 17 at room temperature.…”