Transition-Metal Catalyzed Novel and Useful C-C Bond Formation and Cleavage

过渡金属催化新颖有用的 C-C 键形成和断裂

• 批准号: 11450351
• 负责人: TAMARU Yoshinao
• 金额: $ 9.22万
• 依托单位: Nagasaki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11450351/
• 关键词: palladium; triethlylborane; diethylzinc; allyl alcohol; allylation; alkylation; H2O tolerance; amphiphillic activation; environment; aldehyde; 親電子的アリル化; アリルアルコール; トリエチレンホウ素; 極性転換; アリル化; 活性メチレン化合物; アルキルアルデヒド; 極性転移; アルデヒド

Allyl alcohols are the most useful allyl carbon source, since they are stable, cheep, ubiquitous in nature. However, they have utilized scarcely as C3-unit owing to their low chemical reactivity. This research have disclosed the potential of allyl alcohols as the C-3 unit; they serve not only as allyl cations, but also as allyl anions in the catalytic reactions of palladium in the presence of Et3B or Et2Zn. That is, Pd-Et3B promotes 1) allylation of active methylene compounds, 2) amines, 3) α-position of aldehydes. On the other hand, Pd-Et3B or Pd-Et2Zn helps nucleophilic allylation of aldehydes and ketones by direct use of allyl alcohols themselves. All these reactions proceed at room temperature and even in the presence of water. All these features associated with the use of an allyl alcohol as a starting material combine to contribute to academic advancement, also to creating reactions that are environmentally friendly and economically advantageous.

烯丙醇是最有用的烯丙基碳源，因为它们稳定、廉价、普遍存在于自然界中。然而，由于它们的低化学反应活性，它们很少用作C3-单元。本研究揭示了烯丙醇作为C-3单元的潜力;它们在Et_3B或Et_2Zn存在下不仅作为烯丙基阳离子，而且作为烯丙基阴离子在钯的催化反应中起作用。即Pd-Et 3B促进1）活性亚甲基化合物的烯丙基化，2）胺的烯丙基化，3）醛的α位烯丙基化。另一方面，Pd-Et 3B或Pd-Et 2 Zn通过直接使用烯丙醇本身来帮助醛和酮的亲核烯丙基化。所有这些反应都在室温下甚至在水的存在下进行。所有这些与使用烯丙醇作为起始材料相关的特征结合起来联合收割机有助于学术进步，也有助于产生环境友好和经济上有利的反应。

项目成果

柴田 和文: "Nickel-catalyzed three-component connection reaction of a phenyl group, conjugated dienes, and aldehydes : stereoselective synthesis of(E)-5-phenyl-3-penten-1-ols"J Organimet. Chem.. 624. 348-353 (2001)

Kazufumi Shibata：“镍催化的苯基、共轭二烯和醛的三组分连接反应：(E)-5-苯基-3-戊烯-1-醇的立体选择性合成”J Organimet.. 624。 348-353 (2001)

M. Kimura, T. Tomizawa, Y. Horino, S. Tanaka, Y. Tamaru: "Et_3B- Pd-promoted Allylation of Benzaldehyde with Allylic Alcohols"Tetrahedron Lett.. 41. 3627-3629 (2002)

M. Kimura、T. Tomizawa、Y. Horino、S. Tanaka、Y. Tamaru：“Et_3B-Pd 促进的苯甲醛与烯丙醇的烯丙基化”Tetrahedron Lett.. 41. 3627-3629 (2002)

M. Naito, A. Ezoe, M. Kimura, Y Tamara: "Practical Synthesis of Myrcene Derivatives Possessing Oxidized Methyl Groups"J. Org. Chem. 66. 4447-4449 (2001)

M. Naito、A. Ezoe、M. Kimura、Y Tamara：“具有氧化甲基的月桂烯衍生物的实际合成”J。

Yoshikazu Horino, Masanari Kimura, Shuji Tanaka, Toshiya Okajima Yoshinao Tamaru: "Preparation, Structure, and Unique Thermal [2 + 2], [4 + 2], and [3 + 2] Cycloaddition Reactions of 4- Vinylidene-2-oxazolidinone"Chem. Eur. J.. in press. (2003)

Yoshikazu Horino、Masanari Kimura、Shuji Tanaka、Toshiya Okajima Yoshinao Tamaru：“4-亚乙烯-2-恶唑烷酮的制备、结构和独特的热反应 [2 2]、[4 2] 和 [3 2] 环加成反应”Chem。

田丸良直: "Palladium-Catalyzed Reaction of Allyl and Related Derivatives with Organoelectrophiles in Handbook of Organopalladium Chemistry for Organic Synthesis, E.Negishi, Ed"Wiley. 123 (2002)

Yoshinao Tamaru：“有机合成有机钯化学手册中烯丙基和相关衍生物与有机亲电子试剂的钯催化反应，E.Negishi，Ed”Wiley 123 (2002)。