Recyclable 1,2‐bis[3,5‐bis(trifluoromethyl)phenyl]diselane‐catalyzed oxidation of cyclohexene with H₂O₂: a practical access to trans‐1,2‐cyclohexanediol

Abstract

1,2-Bis[3,5-bis(trifluoromethyl)phenyl]diselane-catalyzed oxidation of cyclohexene by hydrogen peroxide affords a quick, clean and practical access to the important compound trans-1,2-cyclohexanediol under mild conditions. The highly atom-economic properties, clean procedures, high reaction concentration, short reaction time, mild conditions and eco-friendly, recyclable and low loading catalysts facilitate this methodology for possible future practical industrial production.

Water and Aqueous Mixtures as Convenient Alternative Media for Organoselenium Chemistry

“…This was attributed to the presence of a side non-catalyzed reaction that in water can be controlled and thus avoided. The current catalytic species was investigated by NMR, evidencing a peak on 77 Se-NMR that clearly indicates an overoxidized species of selenium (1204 ppm) that was attributed to the peroxyseleninic acid and that, in light of the evidence reported later by Yu et al, could also be assigned to the corresponding peroxyanhydride [54].…”

“…Later the same authors, comparing the reactivity of a number of selenium catalysts using the same methodology, found that 1,2-bis(3,5-bis(trifluoromethyl)phenyl)diselane was the most efficient in terms of yield and reaction rate. In addition, they demonstrate by NMR spectroscopy that in the reaction mechanism the oxygen transfer species, when the precatalyst was diphenyl diselenide, is peroxyseleninic acid [54] ( Figure 13). generated by an undesired ring opening reaction of the epoxide.…”

“…In addition, they demonstrate by NMR spectroscopy that in the reaction mechanism the oxygen transfer species, when the precatalyst was diphenyl diselenide, is peroxyseleninic acid [54] (Figure 13). Previously, it was reported that similar reactions can be performed in a water/MeCN (3:1) mixture using 10% of diphenyl diselenide [55] or water using 2% of selenocysteine at room temperature ( Figure 14) [56].…”

Organoselenium‐Catalyzed Oxidative Ring Expansion of Methylenecyclopropanes with Hydrogen Peroxide

“…On this basis, we envisioned that the oxidative ring expansion of MCPs to cyclobutanones might be achieved by an organoselenium‐catalyzed method by using H 2 O 2 as the oxidant. The organoselenium‐catalyzed oxidation of simple alkenes by H 2 O 2 has already been reported, but its application to the ring expansion of MCPs is still unknown. Given that MCPs are highly active molecules with multiple reaction sites and that the produced cyclobutanones may also undergo further Baeyer–Villiger oxidation, selective oxidation by using the strong oxidant H 2 O 2 faces tremendous challenges (Scheme ).…”

“…Organoselenium catalysts were commercially available or were prepared through known methods. Solvents were analytically pure (AR) and were directly used without any special treatment. All reactions were monitored by TLC.…”