Generation of Ben3yres Using TMP-Zincate

使用 TMP-锌酸盐生成 Ben3yres

• 批准号: 13672205
• 负责人: UCHIYAMA Masanobu
• 金额: $ 2.62万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13672205/
• 关键词: Ate complexes; Ben3yres; Chemoselectivity; 配位環境; オルトメタル化

We have developed new methods for preparing functionalized benzynes through deprotonative zincation as a key reaction using R_2Zn(TMP)Li, and we also describes dramatic ligand effects on the benzyne formation. Deprotonative zincation of various m-substituted bromobenzenes using Me_2Zn(TMP)Li proved effective for the one-pot generation of various 3-functionalized benzynes, particulary those with electrophilic substituents such as ester, amide, and cyano. On the other hand, zincation with ^tBu_2Zn(TMP)Li/ followed by electrophilic trapping (with I_2) proved a powerful tool for the preparation of 1,2,3-trisubstituted aromatic compounds. The resultant 1,2,3-trisubstituted benzenes are available as precursors for generation of 3-substituted benzynes by halogen-zinc exchange reactions using Me_3ZnLi. These methods offer far greater generality than previous methods for the synthesis of functionalized asymmetric benzynes, and should be value in new syntheses of various natural products and functional materials. In addition, these results underline the utility of spectator ligands on the central metal of ate complexes as a tunable functionality in the development of new ate complex-promoted reactions.

我们开发了使用 R_2Zn(TMP)Li 通过去质子锌化作为关键反应来制备官能化苯炔的新方法，并且我们还描述了配体对苯炔形成的显着影响。使用 Me_2Zn(TMP)Li 对各种间位取代的溴苯进行去质子锌化，证明可以有效地一锅法生成各种 3 官能化苯炔，特别是具有亲电取代基（如酯、酰胺和氰基）的苯炔。另一方面，用^tBu_2Zn(TMP)Li/进行锌化，然后进行亲电捕获（用I_2）被证明是制备1,2,3-三取代芳香族化合物的有力工具。所得的 1,2,3-三取代苯可作为使用 Me_3ZnLi 通过卤素-锌交换反应生成 3-取代苯炔的前体。这些方法比以前的功能化不对称苯炔的合成方法具有更大的通用性，并且在各种天然产物和功能材料的新合成中应该具有价值。此外，这些结果强调了ate配合物中心金属上的旁观配体在开发新的ate配合物促进的反应中作为可调功能的效用。

项目成果

Satoshi Nakamura, et al.: "4H-1,2Benzoxazinrs with Electron-withdrawing Substituents on the Benzene Ring"J. Am. Chem. Soc.. 125. 5282-5283 (2003)

Satoshi Nakamura等人：“苯环上具有吸电子取代基的4H-1,2苯并恶嗪”J。

Yuji Imaizumi, Kazuho Sakamoto, Aki Yamada, Aya Hotta, Susumu Ohta, Katsuhiko Muraki, Masanobu Uchiyama, Tomohiko Ohwada: "Molecular Basis of Pimaran Compounds as Novel Activators of Large-Conductance Ca^<2+> - Activated K^+ Cannel α-Subunit"Mol. Pharmaco

Yuji Imaizumi、Kazuho Sakamoto、Aki Yamada、Aya Hotta、Susumu Ohta、Katsuhiko Muraki、Masanobu Uchiyama、Tomohiko Ohwada：“Pimaran 化合物作为大电导 Ca^<2+> 新型激活剂的分子基础 - 激活 K^+ Cannel α -亚基“Mol.Pharmaco”

Tomohiko Ohwada, Masanobu Uchiyama: "Structural Design and Synthesis of Nitric Oxide Donors Aimed to Controlled Release"J. Syn. Org. Chem.. 61. 47-59 (2003)

Tomohiko Ohwada、Masanobu Uchiyama：“旨在控制释放的一氧化氮供体的结构设计与合成”J。

Satoshi Nakamura, Masanobu Uchiyama. Tomohiko Ohwada: "4H-1, 2-Benzoxazines with Electron-withdrawing Substituents on the Benzene Ring. Synthesis and Application as Potent Intermediates for Oxygen-Functionalized Aromatic Compounds"J. Am, Chem. Soc.. 125.

中村聪、内​​山正信。

Yuji Imaizumi, et al.: "Molecular Basis of Pimaran Compounds as Novel Activators of Large Conductance Ca^<2+>-Activated"Mol. Pharmacol. 62. 836-846 (2002)

Yuji Imaizumi等人：“Pimaran化合物作为大电导Ca^2-活化的新型活化剂的分子基础”Mol。