Novel aromatization reaction of enamines employing Pd (II) complex

使用 Pd (II) 配合物的烯胺新型芳构化反应

• 批准号: 10450342
• 负责人: SAITO Seiki
• 金额: $ 8.64万
• 依托单位: Okayama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-10450342/
• 关键词: aromatization of enamine; aromatization of acyclic enone; aniline derivative; PdCl_2; nitro aldol reaction; Mannich reaction

Enamines prepared from cyclohexanones, cyclohexane-1, 3-diones or tetralones led to aryl amines in one pot when treated with stoichiometric amount of palladium salts [PdCl_2 (MeCN)_2] in acetonitrile in the presence of triethylamine at rt or at elevated temperature in some cases for 5 min-2 h. Initial electrophilic attack of palladium chloride on the β-carbon of the enamines led to a σ-palladium species which triggered a series of reactions destined for aromatization to give aryl amines in good yields. The intervention of such a σ-palladium species has been attested by a trapping experiment. On the basis of this reaction mechanism, we have developed another new process capable of transforming acyclic compounds having 6-en-2-one frameworks to aryl amines when their enamines were treated under the similar conditions as above, featuring again the formation of σ-palladium species as the initial key intermediate.

由环己酮、环己烷-1，3-二酮或四氢萘酮制备的烯胺，在乙腈中与化学计量的钯盐[PdCl_2（MeCN）_2]在三乙胺存在下于室温或在某些情况下在高温下反应5 min ~ 2 h，一锅生成芳胺。氯化钯对烯胺的β-碳的亲电攻击导致σ-钯物种，其引发一系列预定芳构化的反应，以良好的产率得到芳基胺。这种σ-钯物种的干预已经通过捕获实验得到证实。根据这一反应机理，我们开发了另一种新的方法，该方法能使具有6-烯-2-酮骨架的无环化合物在与上述类似的条件下，将其烯胺转化为芳胺，其特征仍然是形成作为起始关键中间体的σ-钯物种。

项目成果

Teruhiko Ishikawa,Eiji Uedo,Rie Tani,Seiki Saito: "Aromatization of Enamines Promoted by a Stoichiometric Amount of Palladium (II) Salts : A Novel Method for the Synthesis of Aromatic Amines"J.Org.Chem.. 66・1. 186-191 (2001)

Teruhiko Ishikawa、Eiji Uedo、Rie Tani、Seiki Saito：“化学计量的钯 (II) 盐促进烯胺的芳香化：芳香胺合成的新方法”J.Org.Chem.. 66・1。 -191 (2001)

Teruhiko Ishikawa,Ryuichiro Kadoya,Masaki Arai,Haruka Takahashi,Yumi Kaisi,Tomohiro Mizuta.Kazusa Yoshikai and Seiki Saito: "Revisiting [3+3] Route to 1,3-Cyclohexanedione Frameworks : Missing Opportunity in Organic Synthesis for Sixty Years and Hidden As

Teruhiko Ishikawa、Ryuichiro Kadoya、Masaki Arai、Haruka Takahashi、Yumi Kaisi、Tomohiro Mizuta.Kazusa Yoshikai 和 Seiki Saito：“重访 [3 3] 1,3-环己二酮框架路线：有机合成六十年中错失的机会和隐藏的问题

斎藤清機、石川彰彦: "隣接ジオール制御素子による不斉空間の構築とニトロンーオレフィン[3+2]環化付加反応の立体制御への応用"有機合成化学協会誌. 56. 86-95 (1998)

Seiki Saito，Akihiko Ishikawa：“使用相邻二醇控制元件构建不对称空间及其在硝酮-烯烃[3+2]环加成反应立体控制中的应用”有机合成化学学会杂志 56. 86-95（ 1998）

Seiki Saito and Teruhiko Ishikawa: "Asymmetric Bias Generated by Protected Vicinal Diol Controller and Its application to Asymmetric Nitrone-Olefin Cyycloaddition Reactions"J.Syn.Org.Chem.Jpn.. 56. 86-95 (1998)

Seiki Saito 和 Teruhiko Ishikawa：“受保护的邻位二醇控制器产生的不对称偏差及其在不对称硝酮-烯烃环加成反应中的应用”J.Syn.Org.Chem.Jpn.. 56. 86-95 (1998)

Ishikawa, T. ; Kudoh, T. ; Shigemori, K. ; Saito, S.: "Application of the Silicon-Tether Strategy for Controlling the Regioselectivity and Diastereoselectivity of Intramolecular Nitrone Cycloadditions for Aminopolyol Synthesis."J.Am.Chem.Soc.. 112. 7633-7

石川，T.；