N-tert-Butylbenzenesulfenamide-catalyzed oxidation of alcohols to the corresponding carbonyl compounds with N-chlorosuccinimide

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• 作者：Matsuo ; Jun-ichi ; Iida ; Daisuke ; Yamanaka ; Hiroyuki ; Mukaiyama ; Teruaki
• 关键词：oxidation ; alcohols ; catalysis
• 刊名：Tetrahedron
• 出版年：2003
• 出版时间：August 25, 2003
• 年：2003
• 卷：59
• 期：35
• 页码：6739-6750
• 全文大小：352 K

文摘

N-tert-Butylbenzenesulfenamide (<inter-ref locator=""S0040402003004794/1"" locator-type=""sid"">1</inter-ref>)-catalyzed oxidation of various primary and secondary alcohols to the corresponding aldehydes and ketones was efficiently carried out by using N-chlorosuccinimide (NCS) in the coexistence of potassium carbonate and molecular sieves 4Å at easy-to-control temperatures ranging from 0°C to room temperature. The present catalytic oxidation was performed without giving any damage to the functional groups in alcohols, and was particularly effective in the oxidation of alcohols that formed labile aldehydes because of its mild reaction conditions. Further, selective oxidation of primary hydroxy groups took place in <inter-ref locator=""S0040402003004794/1"" locator-type=""sid"">1</inter-ref>-catalyzed oxidation of several diols. Mechanistic investigation suggested that the chlorination of the sulfenamide <inter-ref locator=""S0040402003004794/1"" locator-type=""sid"">1</inter-ref> by NCS led to the formation of a key species, N-tert-butylbenzenesulfinimidoyl chloride (<inter-ref locator=""S0040402003004794/2"" locator-type=""sid"">2</inter-ref>), which in turn oxidized alcohols in the presence of potassium carbonate to afford carbonyl products by accompanying regeneration of the catalyst <inter-ref locator=""S0040402003004794/1"" locator-type=""sid"">1</inter-ref>.