APPLICATION OF SOLID PHASE HETEROCYCLIC SYNTHESIS USING ORGANOMETALLICS

有机金属固相杂环合成的应用

• 批准号: 12557198
• 负责人: KONDO Yoshinori
• 金额: $ 8万
• 依托单位: TOHOKU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12557198/
• 关键词: ORGANOMETALLICS; SOLID PHASE SYNTHESIS; CHEMOSELECTIVE METALATION; HETEROCYCLIC COMPOUNDS; INDOLE DERIVATIVES; POLYMER SUPPORT; PALLADIUM CATALYST; CARBON-CARBON BOND FORMATION; 複素環化合物; 固相反応; メタル化; インドール; 炭素-炭素結合生成; アート錯体; ポリアー担体

Solid phase synthesis of heterocyclic compounds was investigated using organometallic reagents. Among them, nitrogen heteroaromatics such as indoles, pyridines were chemoselectively metalated using various organometallic reagents and it was found that mesityllithium works as a chemoselective deprotonating agent for solid phase metalation. Scope and limitation was disclosed for the solid phase deprotonation and the reactions with various electrophiles were also examined. Stabilization of the intermediary immobilized oragnometallic species was examined using spectroscopic measurements. As an application of the metalation, the combination with palladium catalyzed reactions was studied and new indole cyclizations using intramolecular palladium catalyzed coupling reaction were also developed. Approaches for high throughput synthesis were investigated using a automated synthesizer and the usefulness of the polymer supported chemistry was demonstrated.

研究了有机金属试剂固相合成杂环化合物的方法。其中，氮杂环化合物，如吲哚，吡啶化学选择性金属化使用各种有机金属试剂，发现mesityllithium工程作为化学选择性去质子化剂固相金属化。揭示了固相去质子化的范围和局限性，并考察了与各种亲电试剂的反应。使用光谱测量来检查中间固定的有机物种类的稳定性。作为金属化反应的一个应用，我们研究了金属化反应与钯催化反应的结合，并开发了新的分子内钯催化偶联吲哚环化反应。使用自动合成仪研究了高通量合成的方法，并证明了聚合物支撑化学的有用性。

项目成果

M.Shilai,Y.Kondo,T.Sakamoto: "Selective Metallation of Thiophene and Thiazole Rings with Magnesium Amide Base"J.Chem.Soc.,Perkin Trans.1. 442-444 (2001)

M.Shilai，Y.Kondo，T.Sakamoto：“噻吩和噻唑环与氨基镁基的选择性金属化”J.Chem.Soc.，Perkin Trans.1。

Yamazaki, K., Kondo, Y.: "Palladium-Catalyzed Synthesis of Indole-3-Carboxylates on a Solid Polymer Support"J. Comb. Chem.. (in press).

Yamazaki, K., Kondo, Y.：“固体聚合物载体上钯催化合成吲哚-3-羧酸盐”J。

Yamazaki, K., Kondo, Y.: "Immobilized α-diazo phosphonoacetate as a versatile Rrg precursor for palladium catalyzed indole synthesis on a polymer support"Chem. Commun. 210-211 (2002)

Yamazaki, K., Kondo, Y.：“固定化 α-重氮膦酰基乙酸酯作为钯催化吲哚合成的通用 Rrg 前体”Chem. 210-211 (2002)

K.Yamazaki, Y.Kondo: "Immobilized a-diazophosphonoacetate as a versatile key precursor for palladium catalyzed indole synthesis on a polymer support"Chem. Comm.. 210-211 (2001)

K.Yamazaki、Y.Kondo：“固定化的 a-重氮膦酰基乙酸盐作为聚合物载体上钯催化吲哚合成的多功能关键前体”Chem。

K.Yamazaki, Y.Kondo: "Palladium-Catalyzed Synthesis of Indole-3-carbokylates on Solid Polymer Support"J. Comb. Chem. (in press).

K.Yamazaki，Y.Kondo：“固体聚合物载体上钯催化合成吲哚-3-羧酸酯”J。