Boron-Masking Strategy for New Transformations of Organoboronic Acids

有机硼酸新转化的硼掩蔽策略

• 批准号: 19205007
• 负责人: SUGINOME Michinori
• 金额: $ 32.53万
• 依托单位: Kyoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 2007
• 资助国家: 日本
• 起止时间: 2007 至 2010
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-19205007/
• 关键词: 合成有機化学; 有機ボロン酸; クロスカップリング; 反復合成; 保護基; マスキング; アントラニルアミド; オルト位C-H結合活性化; 配向基; 有機合成化学; 1,8-ジアミノナフタレン; ジボリル化; 脱水素ホウ素化; 分枝オリゴアレーン; C-H官能基化; クロスカップリソグ; 繰り返し合成; デンドリマー; オリゴ(フェニレン-ビニレン)

New methods for the synthesis of highly functionalized organoboronic acids have been developed on the basis of introduction of "masking groups" onto the boron atoms of organoboronic acids by condensation. 1, 8-Diaminonaphthalene served as a highly robust protecting group particularly in Suzuki. Miyaura coupling. The masking group allowed synthesis of oligoarenes via iterative cross-coupling, iterative synthesis of oligo(phenylene-vinylene) s, and facile synthesis of oligoarene-based dendrons. A diboron reagent in which one of the two boron atoms is protected has been prepared and used in the alkyne diboration reaction, leading to regioselective formation of diboration products, which were applicable to stepwise cross-coupling reactions. Condensates of 2-(pirazol-5-yl) aniline(PZA) and anthranilamide(AAM) with organoboronic acids underwent ruthenium-catalyzed ortho-silylation, in which the nitrogen-containing masking groups(PZA and AAM) served as ortho-directing groups, which are easily removable after the reaction. The AAM group also served as a protecting group for the boronyl group in the Suzuki. Miyaura coupling.

基于通过缩合将“掩蔽基团”引入到有机硼酸的硼原子上，开发了合成高度官能化的有机硼酸的新方法。 1, 8-二氨基萘作为高度稳健的保护基团，特别是在铃木公司中。宫浦联轴器。掩蔽基团允许通过迭代交叉偶联合成低聚芳烃、低聚(亚苯基-亚乙烯基)的迭代合成以及基于低聚芳烃的树枝的轻松合成。制备了两个硼原子之一受到保护的二硼试剂，并将其用于炔烃二硼化反应，导致区域选择性形成二硼化产物，适用于逐步交叉偶联反应。 2-(吡唑-5-基)苯胺(PZA)和邻氨基苯甲酰胺(AAM)与有机硼酸的缩合物进行钌催化的邻位甲硅烷基化反应，其中含氮掩蔽基团(PZA和AAM)作为邻位导向基团，反应后很容易去除。 AAM 基团还充当铃木中硼基基团的保护基团。宫浦联轴器。

项目成果

High-Molecular-Weight Polyquinoxaline-Phosphine (PQXphos) as an Efficient Chiral Ligand for Asymmetric Biaryl Synthesis by Suzuki-Miyaura Coupling

高分子量聚喹喔啉-膦 (PQXphos) 作为一种高效手性配体，用于铃木-宫浦偶联合成不对称联芳基

• 发表时间: 2011
• 期刊: Angew.Chem., Int.Ed.
• 作者: Mori;T.;他;Michinori Suginome
• 通讯作者: Michinori Suginome

Protection of Boronyl Groups for the Synthesis of Functionalized Organoboronic Acid Derivatives

硼基基团的保护用于合成功能化有机硼酸衍生物

• 发表时间: 2009
• 作者: Suginome;M.
• 通讯作者: M.

Transition Metal‐Catalyzed Element‐Boryl Additions to Unsaturated Organic Compounds

• DOI: 10.1002/9783527639328.ch3
• 发表时间: 2011-10
• 作者: M. Suginome;Toshimichi Ohmura

Ruthenium-catalyzed C-H Silylation of Methylboronic Acid Using a Removable α-Directing Modifier on the Boron Atom

• DOI: 10.1246/cl.2011.916
• 发表时间: 2011-09-05
• 期刊: CHEMISTRY LETTERS
• 影响因子: 1.6
• 作者: Ihara, Hideki;Ueda, Akinori;Suginome, Michinori
• 通讯作者: Suginome, Michinori

New Metal-Mediated Organic Synthesis by Virtue of New Protecting, Directing, and Reacting Groups on the Boron Atoms of Organoboronic Acids

利用有机硼酸硼原子上的新保护、导向和反应基团进行新金属介导的有机合成

• 发表时间: 2010
• 作者: Suginome;M.
• 通讯作者: M.