STUDY OF POLYMER-SUPPORTED DESS-MARTIN HYPERVALENT IODINE REAGENT

聚合物负载戴斯马丁高价碘试剂的研究

• 批准号: 13554028
• 负责人: TOGO Hideo
• 金额: $ 3.78万
• 依托单位: CHIBA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13554028/
• 关键词: Alcohol; Ketone; Aldehyde; Environmental Benign; Polymer-supported Hypervalent Iodine; リサイクル; カルボン酸; 高分子型超原子価ヨウ素酸化

Primary and secondary alcohols were successfully oxidized to the corresponding aldehydes and ketones at room temperature in good yields, respectively, with poly[4-(diacetoxyiodo)styrene] (PSDIB) in the presence of TEMPO (cat.) in acetone, as an environmentally friendly method. Here, polymer-supported hypervapent iodine was quantitatively recovered by simple filtration from the reaction mixture, and PSDIB was regenerated by treatment with peracetic acid and reused successfully. The previous methods such as Swern oxidation and Dess-Martin oxidation may be substituted by the present method, since the present oxidation of primary and secondary alcohols to the corresponding aldehydes and ketones, respectively, is effective and secure as an operationally simple and environmentally benign method, and can be used for the synthesis of pharmaceutical and agrochemical substances

以聚[4-（二乙酰氧基）苯乙烯]（PSDIB）为原料，在丙酮中以TEMPO （cat.）存在的条件下，在室温下以较好的收率成功地氧化了伯醇和仲醇相应的醛和酮。在这里，聚合物负载的高蒸发碘通过简单过滤从反应混合物中定量回收，PSDIB通过过氧乙酸处理再生并成功重复使用。由于本方法将伯醇和仲醇分别氧化为相应的醛类和酮类，是一种操作简单、环保的有效、安全的方法，可用于医药和农化物质的合成，因此，以前的方法如Swern氧化和Dess-Martin氧化可被本方法所取代

项目成果

S.Abe, K.Sakuratani, H.Togo: "Synthetic Use of Poly[4-hydroxy(tosyloxy)iodo]styrenes"J.Org.Chem.. 66. 6174-6177 (2001)

S.Abe、K.Sakuratani、H.Togo：“聚[4-羟基(甲苯磺酰氧基)碘]苯乙烯的合成用途”J.Org.Chem.. 66. 6174-6177 (2001)

H.Togo, M.Sugi, K.Toyama: "1,1,2,2-Tetraphenyldisilane (TPDS) as a New Diversified Radical Reagent"Compt.Rend.Serie IIc. 539-546 (2001)

H.Togo、M.Sugi、K.Toyama：“1,1,2,2-四苯基二硅烷 (TPDS) 作为新型多样化自由基试剂”Compt.Rend.Serie IIc。

K.Sakuratani, H.Togo: "Environmentaly Friendly TEMPO-mediated Oxidation of Alcohols with Poly[4-(diacetoxyiodo)styrene]"Synthesis. 22-23 (2003)

K.Sakuratani、H.Togo：“环境友好的 TEMPO 介导的聚[4-(二乙酰氧基碘)苯乙烯]醇氧化”合成。

M.Ueno, T.Nabana, H.Togo: "Novel Oxidative a-Tosyloxylation of Alcohols with Iodosylbenzene and p-Toluenesulfonic Acid, and Its Synthetic Application for the Direct"J.Org.Chem.. 68. 6424-6425 (2003)

M.Ueno，T.Nabana，H.Togo：“醇与碘酰苯和对甲苯磺酸的新型氧化α-甲苯磺酰氧基化及其直接合成应用”J.Org.Chem.. 68. 6424-6425 (2003

"Synthetic Use of Poly[4-hydroxy(tosyloxy)iodo]styrenes"J.Org.Chem.. 66. 6174-6177 (2001)

“聚[4-羟基(甲苯磺酰氧基)碘]苯乙烯的合成用途”J.Org.Chem.. 66. 6174-6177 (2001)