Unmatched efficiency and selectivity in the epoxidation of olefins with oxo-diperoxomolybdenum(VI) complexes as catalysts and hydrogen peroxide as terminal oxidant

Synthesis and catalytic epoxidation potentiality of oxodiperoxo molybdenum(VI) complexes with pyridine-2-carboxaldoxime and pyridine-2-carboxylate: the crystal structure of PMePh3[MoO(O2)2(PyCO)]

“…As part of our continued interest in using oxoperoxomolybdenum complexes as oxidation catalysts, we were intrigued by previous reports [26,27] at the failure of the Mo-complexes to activate H 2 O 2 and by using a molybdenum complex, PPh 4 [MoO(O 2 ) 2 (SaloxH)] [6] (SaloxH 2 = Salicylaldoxime) as catalyst along with NaH CO 3 as cocatalyst [28,29] we were able to activate H 2 O 2 and the integrated catalyst, co-catalyst and oxidant functioned as a very efficient peroxidic epoxidation system. Inspired by this result, we reported some other peroxo complexes, which showed higher to much higher catalytic efficiencies [6][7][8][9][10] for olefin epoxidation. In this paper, we report the synthesis, structural characterization, and catalytic epoxidation activities of two oxodiperoxo complexes, [MoO(O 2 ) 2 (PyCOXH) (H 2 O)] (1) (PyCOXH = Pyridine-2-carboxaldoxime) and PMePh 3 [MoO(O 2 ) 2 (PyCO)] (2) (PyCOH = Pyridine-2-carboxylic acid).…”

“…accommodates the bidentate ligands by forming oxomonoperoxo complexes of the type [MO(O 2 )(bidentate) 2 ] (the bold font indicates bulky ligand) [6][7][8]. Recently, it has been shown that the MoO(O 2 ) 2 cores with bidentate ligands are useful catalysts in the epoxidation of olefins [6][7][8][9][10]. Epoxidation of olefins and arenes is an important transformation in organic synthesis since the epoxy compounds are widely used, for example in the manufacture of polyurethanes, unsaturated resins, glycols, surfactants, etc.…”

Oxidation of Alkenes with H2O2 by an in-Situ Prepared Mn(II)/Pyridine-2-carboxylic Acid Catalyst and the Role of Ketones in Activating H2O2

“…Initial limitations imposed by the acidic conditions resulted in restrictions to their application in the formation of acid-sensitive substrates and other substrates such as styrene, but recently, modified conditions toward addressing this issue have been reported. 16,17 In the case of the MTO systems, good conversion and selectivity can be achieved for a range of alkene substrates, in particular, trans-alkenes, albeit with relatively long reaction times (1−20 h). 14,15 Alkene epoxidation and cis-dihydroxylation with manganesebased catalysts has seen rapid progress in recent years also, 18,19 in particular the recent reports by Lau and co-workers with (PPh 4 ) 2 [Mn(IV)(N)(CN) 4 ], 20 and with the manganese triand tetraaza-macrocycle-based complexes developed by De Vos, 21 Berkessel, 22 Busch, 23,24 Costas, 25,26 and our own groups.…”

Transition Metal‐Catalyzed Epoxidation of Alkenes

“…This protocol has not been employed for the formation of hydrolytically sensitive epoxides, and the generality of the method can thus be questioned. A recent example of a highly efficient molybdenum-based protocol for alkene epoxidation using aqueous hydrogen peroxide was developed by Bhattacharyya and coworkers [31]. The use of oxodiperoxomolybdenum(VI) complexes ligated with 8-quinolinol (QOH) allowed for epoxidation of a series of various alkenes.…”