Hypervalent Iodine(III)Compounds in Organic Synthesis

有机合成中的高价碘(III)化合物

• 批准号: 05453182
• 负责人: KITA Yasuyuki
• 金额: $ 4.22万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05453182/
• 关键词: hypervalent iodine(III)compounds; phenyliodine(III)bis(trifluoroacetate)(PIFA); cation radical intermediates; oxidative phenolic coupling; cyclic iodinane; discorhabdin C; spirodienones; lH-azepines; 超原子価ヨウ素試薬; ラジカルカチオン; フェノールカップリング; アザスピロジエノン

In'this project, we have studied on the developement of novel reactions using hypervalent iodine(III)compounds and the application to the synthesis of biologically active natural products.i)We recently developed the novel direct azidation of p-substituted phenol ethers using phenyliodine(III)bis(trifluoroacetate)(PIFA)in polar and low nucleophilic solvents such as CF_3CH_2OH and(CF_3)_2CHOH.We found that the reaction proceeds via cation radical intermediates by UV and ESR spectroscopic studies. The reaction is effective for introductions of oxygen, carbon, and sulfur nucleophiles. We could apply the reaction to the intramolecular oxidative phenolic coupling. On the other hand, in CH_3CN the alkyl azidation occurrs at the benzylic position of p-substituted phenol cthers.ii)Although the reagents having azido or cyano ligands are known to be quite useful for the azidation of various compounds or for other reactions, they are too labile to be isolated. The cyclic iodinanes having azido, cyano, and nitrooxy ligands, which are crystalline and air-stable could be prepared.iii)We recently reported the total synthesis of marine antitumor alkaloid, discorhabdin C by PIFA induced cyclization of p-substituted phenolic aminoquinones. It was found that the cyclization of phenol derivatives bearing aminoquinones at the omicron-or m-position provides a versatile route to spirodienones and lH-azepines. Furthermore, the novel synthetic method for N,S-acetal, which is the essential structure of discorhabdin alkaloids, by the cleavage of the beta-lactam ring was also developed.

在这个项目中，我们研究了使用高价碘（III）化合物的新型反应的开发以及在生物活性天然产物合成中的应用。i)我们最近开发了使用苯碘对对取代苯酚醚进行直接叠氮化的新型方法(III)双(三氟乙酸)(PIFA)在极性和低亲核溶剂如CF_3CH_2OH和(CF_3)_2CHOH中。我们发现该反应通过紫外和 ESR 光谱研究通过阳离子自由基中间体进行。该反应对于引入氧、碳和硫亲核试剂是有效的。我们可以将该反应应用于分子内氧化酚偶联。另一方面，在 CH_3CN 中，烷基叠氮化反应发生在对位取代苯酚基团的苄基位置。ii)尽管已知具有叠氮基或氰基配体的试剂对于各种化合物的叠氮化反应或其他反应非常有用，但它们太不稳定而无法被孤立。可以制备具有叠氮基、氰基和硝基氧基配体的环状碘烷，其是晶体且空气稳定的。iii)我们最近报道了通过PIFA诱导对位取代酚氨基醌环化来全合成海洋抗肿瘤生物碱discorhabdin C。发现在微米位或间位带有氨基醌的苯酚衍生物的环化提供了制备螺二烯酮和1H-氮杂平的通用途径。此外，还开发了通过β-内酰胺环裂解合成N,S-缩醛的新方法，N,S-缩醛是discorhabdin生物碱的基本结构。

项目成果

Shuji Akai,et al.: "Preparation of Novel Cyclic Hypervalent Iodine (III) Compounds Having Azido,Cyano,and Nitrato Ligands" Heterocyles. 42. 47-51 (1996)

Shuji Akai 等人：“具有叠氮基、氰基和硝基配体的新型环状高价碘 (III) 化合物的制备”杂环。

Yasuyuki Kita: "An Unprecedented Cleavage of β-Lactam Ring:Stereoselective Synthesis of Chiral β-Amidocyanides" J.Org.Chem.,. (in press). (1994)

Yasuyuki Kita：“β-内酰胺环的前所未有的裂解：手性 β-氨基氰化物的立体选择性合成”J.Org.Chem.，（出版中）。

Y.Kita, H.Tohma, K.Hatanaka, T.Takada, S.Fujita, S.Mitoh, H.Sakurai and S.Oka: "Hypervalent Iodine Induced Nucleophilic Substitution of p-Substituted Phenol Ethers. Generation of Cation Radicals as Reactive Intermediates" J.Am.Chem.Soc.116. 3684-3691 (199

Y.Kita、H.Tohma、K.Hatanaka、T.Takada、S.Fujita、S.Mitoh、H.Sakurai 和 S.Oka：“高价碘诱导对位取代苯酚醚的亲核取代。阳离子自由基的生成为

Yasuyuki Kita: "Preparation of Bis(arylthio)iodobenzene and Reaction with 1-Alkynes.A Novel Route to 1,2-Bis(arylthio)alkenes" Tetrahedron Lett.,. (in press). (1994)

Yasuyuki Kita：“双（芳硫基）碘苯的制备及其与 1-炔烃的反应。1,2-双（芳硫基）烯烃的新路线”Tetrahedron Lett.,。

S Akai et al.,: "Preparation of Novel Cyclic Hypervalent Iodine(III)Compounds Having Azido,Cyano,and Nitrato Ligands" Heterocycles. 42. 47-51 (1996)

S Akai 等人：“具有叠氮基、氰基和硝基配体的新型环状高价碘 (III) 化合物的制备”杂环。