Development of the novel C-C bond forming reactions using homogeneous transition metal catalysts

使用均相过渡金属催化剂开发新型 C-C 键形成反应

• 批准号: 09304069
• 负责人: YAMAMOTO Yoshinori
• 金额: $ 25.92万
• 依托单位: TOHOKU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09304069/
• 关键词: Enynes; Diynes; Alkynes; Palladium; Cycloaddition; Benzene; パラジウム触媒; 共役エンイン; 芳香環化; スチレン誘導体; フェノール誘導体; フラン誘導体; シクロファン; ヘテロ環; プロ求核剤; アレン

Monosubstituted conjugated enynes were found to undergo [4+2] homodimerization smoothly in the presence of palladium catalyst to give 4, α-and 2,6-disubstituted styrene derivatives. Analogous cross-cycloaddition of conjugated enynes and diynes was also developed to afford a variety of polysubstituted benzenes, including phenol and aniline derivatives. Alkynes and diynes in the presence of a palladium catalyst underwent novel formal [2+2+2] sequential cyclotrimerization to afford multifunctional benzenes in one step with high degrees of regio- and chemoselectivities. Mechanism of these novel transformations was proposed.

发现单取代的共轭烯炔在钯催化剂存在下顺利进行[4+2]均二聚，得到4,α-和2,6-二取代的苯乙烯衍生物，还开发了共轭烯炔和二炔的类似交叉环加成反应。各种多取代苯，包括苯酚和苯胺衍生物，在存在的情况下。钯催化剂追求新型形式的[2+2+2]顺序环三聚，以一步提供具有高度区域和化学选择性的多功能苯，并提出了这些新型转化的机制。

项目成果

J.-G.Shim,Y.Yamamoto: "A Novel and Effective Route to 1,3-Oxazolidine Derivatives. Palladium Catalyzed Regioselective [3+2] Cycloaddition of Vinylic Oxyranes with Imines"Tetrahedron Lett. 40. 1053-1056 (1999)

J.-G.Shim，Y.Yamamoto：“一种新颖且有效的 1,3-恶唑烷衍生物路线。钯催化的区域选择性 [3 2] 乙烯基环氧乙烷与亚胺的环加成”四面体莱特。

Vladimir Gerorgyan: "Regiospeccific Synthesis of Polysubstituted Phorols via the Palladium-Catalyzed Enyre-Diyne[4+2]Cross-Berzannulation Pathray" The Journal of Organic Chemistry. 63. 1244-1247 (1998)

Vladimir Gerorgyan：“通过钯催化 Enyre-Diyne[4 2]Cross-Berzannulation Pathray 进行多取代佛罗醇的区域特异性合成”有机化学杂志。

I.Kadota,A.Shibuya,L.Lutete,Y.Yamamoto: "Palladium/Benzoic Acid Catalyzed Hydroamination of Alkynes"J.Org.Chem.. 64. 4570-4571 (1999)

I.Kadota，A.Shibuya，L.Lutete，Y.Yamamoto：“钯/苯甲酸催化炔烃的氢氨化”J.Org.Chem.. 64. 4570-4571 (1999)

Douglas Weibel: "Synthesis of Polyethor Exomothylene Paracydophanes viaan Intranolecular Pd-Catalyzed Bis-Enyne Bnzannulation Protocol" The Journal of Orgaic Chemistry. 63. 1217-1220 (1998)

Douglas Weibel：“通过分子内 Pd 催化双烯炔 Bnzannulation 方案合成聚乙醚外乙烯对乙酰基”有机化学杂志。

V.Gevorgyan,Y.Yamamoto: "Perspectives in Organopalladium Chemistry for the 21 Century"Elsevier. 16 (1999)

V.Gevorgyan、Y.Yamamoto：“21 世纪有机钯化学展望”Elsevier。