Mechanism and Scope of the Mn-III-Initiated Oxidation of beta-Ketocarbonyl Compounds: Furan Synthesis

作者：Wang, Chao; Li, Zhilong; Ju, Yeming; Koo, Sangho^*

来源：European Journal of Organic Chemistry, 2012, 2012(35): 6976-6985.

DOI：10.1002/ejoc.201201194

• Reaction mechanisms
• Cyclization
• Oxygen heterocycles
• Radicals
• Manganese
• Oxidation

Unless the Mn-III-produced carbon-radical from beta-ketocarbonyl compounds undergoes smooth intramolecular addition to alkenes, it traps molecular oxygen in the reaction medium to produce a peroxy radical, which reacts with the neighbouring carbonyl group to form 1,2-dioxetane. Thermal decomposition of 1,2-dioxetane completes the oxidation to produce alpha-oxo ester. This oxidation seems to be general at 50 degrees C under aerobic conditions, and can be catalytic for Mn-III in AcOH with ultrasonic irradiation. Thus, the development of a new synthetic method for diversely substituted furans has been accomplished based on a couple of the Mn-III-initiated domino oxidation of beta-ketocarbonyl compounds with a suitable alpha-allylic substitution.

• 出版日期2012-12
• 单位华东理工大学