Biomimetic alkane oxidation by iodosylbenzene and iodobenzene diacetate catalyzed by a new manganese porphyrin: Water effect

Exploring manganese pyridylporphyrin isomers for cyclohexane oxidation: First‐generation catalysts are better than third‐generation ones

“…[85] In the same way, water can also be used as a cocatalyst, as described in the literature. [39,86,87] At first, we verified the effect of water in the oxidation of cyclohexane by PhI(OAc) 2 (Figure 7 and Table S2). Reactions with the first-generation isomers 1, 2, and 3 exhibited a slight increase in the total yield when compared to the systems without this additive.…”

New highly brominated Mn-porphyrin: a good catalyst for activation of inert C–H bonds

“…5) gave slightly higher total product yield than those veried by Groves et al (12% 1-Adol and 1% 2-Adol). 7 Cat.1 was also more efficient than the catalyst cis-[Mn III DAPDPP]Cl proposed by Silva et al 72 Compared with Cat.1, the catalyst [Mn III PFTDCPP]Cl obtained by Doro et al was much more efficient (35% 1-Adol, 10% 2-Adol, and 5% 2-Adone). 12 In the latter MnP, the electron withdrawing substituents (uoro and chloro) in the ortho-, meta-, and para-mesoaryl positions of the macrocycle must have rendered the high-valent active species more reactive.…”

“…Compared with Cat.1, the second-generation cis-[Mn III DAPDPP]Cl, which bears amino groups in the paramesoaryl positions of the porphyrin ring, is more selective for the alcohols ($71%). 72 The amino groups in cis-[Mn III DAPDPP]Cl may have coordinated with the metal center of another cis-[Mn III DAPDPP]Cl, to render the high-valent active species Mn V (O) P more reactive and to elevate the selectivity toward the alcohol. 27 Compared with the third-generation catalyst derived from cis- [Mn III DAPDPP]Cl, 72 Cat.2 was more selective ($74 and $81%, respectively).…”

“…72 The amino groups in cis-[Mn III DAPDPP]Cl may have coordinated with the metal center of another cis-[Mn III DAPDPP]Cl, to render the high-valent active species Mn V (O) P more reactive and to elevate the selectivity toward the alcohol. 27 Compared with the third-generation catalyst derived from cis- [Mn III DAPDPP]Cl, 72 Cat.2 was more selective ($74 and $81%, respectively). The MnP/PhI(OAc) 2 and the MnP/PhIO systems gave similar total product yield and selectivity, but Cat.2 was always slightly more prone to oxidative destruction than Cat.1.…”

Catalyst-free and solvent-free oxidation of cycloalkanes (C5-C8) with molecular oxygen: Determination of autoxidation temperature and product distribution

“…In addition, cycloalkanols and cycloalkanones are important intermediates and solvents in the chemical industry and academic research [25][26][27][28][29][30][31]. To realize this necessary transformation from cycloalkanes to their oxidized products, several oxidants can be employed, such as iodosylbenzene [32][33][34][35][36][37][38], iodosylbenzene diacetate [34,[38][39][40], tert-butyl hydroperoxide [41][42][43][44][45][46][47][48][49], m-chloroperoxybenzoic acid [50][51][52][53][54][55], hydrogen peroxide [56][57][58][59][60][61][62][63], molecular oxygen [64][65][66][67][68][69][70]…”