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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  
  选自 期刊  European Journal of Organic Chemistry;  卷期  2012年-35;  页码  6976-6985  
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[摘要]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.

 
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