Reactions with Manganese (III) Acetate

Heterogeneous Permanganate Oxidations. 7. The Oxidation of Aliphatic Side Chains

“…Predicting the fate of the manganese(III) product produced from the cleavage reaction depicted in Scheme is more difficult. It could either be reduced by the solvent to give manganese(II) or oxidized by excess oxidant to manganese dioxide …”

Synthesis of substituted tetrahydronaphthalenes by manganese(III), cerium(IV), and iron(III) oxidation of substituted diethyl .alpha.-benzylmalonates in the presence of olefins

“…The only exceptions are the o-phenyl derivative lk, which affords in high yield the dihydrophenanthrene derivative 4 (eq 2), and the diethyl a-(l-phenylethyl)malonate (lm), which gives moderate yield of 3 in a slow reaction. + 2MLm + 2HL (2) Substituents in meta position direct the cyclization at the ortho and para positions and steric hindrance inhibits the formation of the ortho product.® Only traces of products coming from the free-radical chain addition7 of malonic ester 1 to olefins 2 (XPhCH2C-(COOEt)2CHR1CHR2R3) are observed. The reaction rates are only marginally affected by substituents, except with substrates lk or lm, for which the reaction is faster or slower than with other substrates, respectively.…”

“…However, some limits, not related to the initial oxidation of the malonate ester, are apparent. They are due to (1) fast intramolecular addition processes to «--systems without olefin addition, (2) allylic oxidation of olefins, and (3) formation of open-chain addition products to the olefin. The dependence of the yield of reaction 1 and side reactions upon the structure of malonic ester, metal oxidants, and substituents on the olefin point to a common mechanism, despite the different metal, ligand, and solvent used (Scheme I).…”

Selective Oxidation of Acetophenones Bearing Various Functional Groups to Benzoic Acid Derivatives with Molecular Oxygen

“…[10,14] On the other hand, it is well-known that MnA C H T U N G T R E N N U N G (III) species such as MnA C H T U N G T R E N N U N G (OAc) 3 possess a high one-electron oxidation ability for enolizable compounds like ketones to give a free radical which then reacts with O 2 or adds to alkenes and alkynes. [15] In addition, MnA C H T U N G T R E N N U N G (OAc) 2 is oxidized to MnA C H T U N G T R E N N U N G (OAc) 3 in acetic acid under the influence of O 2 and ketone. [15] In fact, we have reported that on the MnA C H T U N G T R E N N U N G (OAc) 2 -catalyzed oxidative radical addition of enolizable compounds to afford unsaturated systems.…”

“…[15] In addition, MnA C H T U N G T R E N N U N G (OAc) 2 is oxidized to MnA C H T U N G T R E N N U N G (OAc) 3 in acetic acid under the influence of O 2 and ketone. [15] In fact, we have reported that on the MnA C H T U N G T R E N N U N G (OAc) 2 -catalyzed oxidative radical addition of enolizable compounds to afford unsaturated systems. [16] [a] 1 (3 mmol) was allowed to react in the presence of THICA (5 mol%), CoA C H T U N G T R E N N U N G (OAc) 2 (0.5 mol%), and MnA C H T U N G T R E N N U N G (OAc) 2 (0.5 mol%) under O 2 (1 atm) in AcOH (3 mL) at 120 8C for 15 h. [b] Yields based on GC analysis after the esterification with MeOH (20 mL) and H 2 SO 4 (50 mg) at 100 8C for 24 h. Numbers in parenthesis show isolated yields.…”