Iodine-Initiated Dioxygenation of Aryl Alkenes Usingtert-Butylhydroperoxides and Water: A Route to Vicinal Diols and Bisperoxides

Abstract

An environment-friendly and efficient dioxygenation of aryl alkenes for the construction of vicinal diols has been developed in water with iodine as the catalyst and tert-butylhydroperoxides (TBHPs) as the oxidant. The protocol was efficient, sustainable, and operationally simple. Detailed mechanistic studies indicated that one of the hydroxyl groups is derived from water and the other one is derived from TBHP. Additionally, the bisperoxides could be obtained in good yields with iodine as the catalyst, Na2CO3 as the additive, and propylene carbonate as the solvent, instead.

Synthesis of α/β-Aromatic Peroxy Thiols Mediated by Iodine Source

“…Based on the above research and relevant literature reports, − we propose a reasonable reaction mechanism (Scheme ). First, NH 4 I and I 2 interact with TBHP to form tert -butoxy and iodine radicals.…”

A Short and Facile [2 + 2] Photocycloaddition Protocol Toward Construction of a Levuglandin Skeleton

“…In the literature, numerous methods for the oxidation of olefins using various reagents have been reported. [18][19][20][21][22][23][24][25] We chose potassium permanganate in THF-water for the vicinal dihydroxylation of 11 as reported by Simandi and colleagues. 26,27 Thus the mixture of cyclobutenes 11 and 14 was treated with potassium permanganate in THF-water at room temperature.…”

TBAI-Catalyzed Regioselective Hydroxyperoxidation of 1-Aryl/Alkyl-1,3-dienes

“…Difunctionalization of alkenes via introduction of two different functional groups is an important transformation in organic synthesis to build molecular complexity in a single operation . In recent years, there has been considerable interest in regio-divergent heterodifunctionalization of alkenes by introducing a peroxide group along with other different functional groups. − The synthesis of organic peroxides have always attracted considerable attention as these are highly valuable and interesting compounds, widely present in several bioactive natural products and pharmaceutically important molecules . Over the years while several approaches have been reported for the development of functionalized peroxides, the need for mild, economical, and metal-free transformations goes unabated .…”

“…Over the years while several approaches have been reported for the development of functionalized peroxides, the need for mild, economical, and metal-free transformations goes unabated . Different strategies have been established for difunctionalization of alkenes with tert -butyl hydroperoxide (TBHP), such as carbonylative-peroxidation, carbo-peroxidation, nitrogen-peroxidation, silicon-peroxidation, phosphate-peroxidation, halo-peroxidation, thio-peroxidation, bis-peroxidation, and hydroxyl-peroxidation . An efficient protocol was developed by Li for synthesis of β-peroxy ketones 3a via carbonylative-peroxidation of alkenes 1 using aldehydes 2 , hydroperoxide, and catalyzed by iron (Scheme A) .…”