344349-72-0

Upstream product

• 66336-42-3 8-methyl-1,4-dioxa-spiro[4.5]decan-8-ol 
• 4746-97-8 cyclohexanedione monoethylene ketal 
• 89794-52-5 1-methyl-1,4-cyclohexanediol 
• 98-88-4 benzoyl chloride 
• 17429-02-6 4-hydroxy-4-methylcyclohexanone 

Relevant academic research and scientific papers

A unified photoredox-catalysis strategy for C(sp3)-H hydroxylation and amidation using hypervalent iodine

We report a unified photoredox-catalysis strategy for both hydroxylation and amidation of tertiary and benzylic C-H bonds. Use of hydroxyl perfluorobenziodoxole (PFBl-OH) oxidant is critical for efficient tertiary C-H functionalization, likely due to the enhanced electrophilicity of the benziodoxole radical. Benzylic methylene C-H bonds can be hydroxylated or amidated using unmodified hydroxyl benziodoxole oxidant Bl-OH under similar conditions. An ionic mechanism involving nucleophilic trapping of a carbocation intermediate by H2O or CH3CN cosolvent is presented.

Dependence of intramolecular dissociative electron transfer rates on driving force in Donor-Spacer-Acceptor systems

The voltammetric reduction of a series of phenyl-substituted 4- benzoyloxy-1-methylcyclohexyl bromides has been investigated in DMF. The reduction leads to the cleavage of the C-Br bond. On a thermodynamic ground, the direct reduction of the tertiary C-Br function is easier than that of the selected benzoates by at least 0.5 V. However, since the direct reduction of bromides is affected by a large activation overpotential, the electron is first located in the benzoate moiety. The rate constant for the following exergonic intramolecular dissociative electron transfer was determined by kinetic analysis of the cyclic voltammetry curves. The intermolecular rate constants for the reaction between the radical anions of methyl benzoates and 4-tert-butyl-1-methylcyclohexyl bromide were also determined and found to correlate very well with related literature data pertaining to tert-butyl bromide. The intramolecular rate constants were found to be more sensitive to variation of driving force than the corresponding intermolecular data. This result can be attributed to a shift of the center of the π* orbital of the radical anion donor away from the acceptor moiety, the shift being larger for the most easily reduced donors. The resulting distance increase is therefore envisaged as responsible for a more rapid rate drop, compared to the intermolecular pattern, when smaller driving forces are considered.