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，我们研究了高价碘（III）化合物的新反应及其在生物活性天然产物合成中的应用：i）我们最近开发了一种新的邻取代苯酚醚的直接叠氮化反应，在极性和低亲核性溶剂如CF_3CH_2OH和（CF_3）_2中，通过紫外光谱和电子自旋共振（ESR）光谱研究发现，反应是通过阳离子自由基中间体进行的。该反应对于引入氧、碳和硫亲核试剂是有效的。该反应可应用于分子内氧化酚偶联反应。另一方面，在CH_3CN中，对位取代酚醚的苄基位发生烷基叠氮化反应。ii）虽然已知具有叠氮基或氰基配体的试剂对各种化合物的叠氮化反应或其它反应是非常有用的，但它们太不稳定而不能分离。三）我们最近报道了海洋抗肿瘤生物碱discorhabdin C的全合成，通过PIFA诱导的环化的p-取代酚氨基醌。发现在ω-或m-位上带有氨基醌的苯酚衍生物的环化提供了一条合成螺二烯酮和IH-氮杂卓的通用路线。此外，还发展了通过β-内酰胺环断裂合成discorhabdin生物碱的基本结构N，S-缩醛的新方法。

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）。

Yasuyuki Kita,et al.: "Hypervalent Iodinc Induced Nucleophilic Substitution of para-Substiuted Phenol Ether. Gencration of Cation Radicals as Reactive Intermediates" J. An. Chem. Soc.116. 3684-3691 (1994)

Yasuyuki Kita 等人：“高价碘诱导对位取代苯酚醚的亲核取代。作为反应中间体的阳离子自由基的生成”J. An。

S.Akai, T.Okuno, M.Egi, T.Takada, H.Tohma, and Y.Kita: "Preparation of Novel Cyclic Hypervalent Iodine(III)Compounds having Azido, Cyano, and Nitrato Ligands" Heterocycles. 42. 47-51 (1996)

S.Akai、T.Okuno、M.Egi、T.Takada、H.Tohma 和 Y.Kita：“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。

Y,Kita et al.,: "An Intramolecular Cyclization of Phenol Derivatives Bearing Aminoquinones Using a Hypervalent Iodine Reagent" J.Org,Chem.61. 223-227 (1996)

Y，Kita 等人，：“使用高价碘试剂对带有氨基醌的苯酚衍生物进行分子内环化”J.Org，Chem.61。