Novel Reactivity of Main Group Alkynylmetals and Its Application to Organic Synthesis

主族炔基金属的新反应性及其在有机合成中的应用

• 批准号: 11650892
• 负责人: HARADA Toshiro
• 金额: $ 2.3万
• 依托单位: Kyoto Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650892/
• 关键词: Alkyne; Alkynylmetal; Tandem Cyclization; Cycloisomerization; C-H Insertion; Carbon-carbon Bond Formation; Main Group Metal; Carbenoid; カルベン; 挿入反応; 環化反応

1-Alkynyl organometallics of main group metals have been frequently used as efficient carbon nucleophiles in organic syntheses. They react with a variety of electrophilic reagents generally at the carbon α to the metal atom. In order to develop a convergent method for the construction of complex carbon frameworks, a hitherto unexplored nucleophilic reactivity of alkynylmetals at the β position is investigated. The study reveals that various alkynylmetals react at the β position especially in intramolecular reactions. Alkynylzincates bearing a remote leaving group undergo smooth exo-cyclization at the β position with simultaneous 1, 2-migration of a ligand on the zinc atom to give 1-(cycloalkylidene) alkylzinc reagents, which can be used in subsequent reactions with electrophiles. Alkynylmetals of lithium, sodium, and potassium also undergo exo-cyclization to give cycloalkylidene carbene. A method for the synthesis of polycyclic compounds is developed utilizing the exo-cyclization of alkynylmetals and intramolecular C-H insertion of the resulting carbenes.

1-炔基金属有机化合物是有机合成中常用的高效碳亲核试剂。它们通常在金属原子的α碳上与各种亲电试剂反应。为了发展一种用于构建复杂碳骨架的收敛方法，研究了迄今为止尚未探索的炔基金属在β位的亲核反应性。研究表明，各种炔基金属在β位反应，特别是在分子内反应。带有远程离去基团的炔基锌酸盐在β位上进行顺利的外环化，同时锌原子上的配体发生1，2-迁移，得到1-（环烷叉）烷基锌试剂，该试剂可用于与亲电试剂的后续反应。锂、钠和钾的炔基金属也进行外环化以得到环烷叉卡宾。发展了一种利用炔基金属的外环化和所得卡宾的分子内C-H插入来合成多环化合物的方法。

项目成果

Toshiro Harada: "Practical Approach in Organozinc Chemistry (invited chapter)"Oxford University Press. 101-116 (1999)

原田敏郎：《有机锌化学实用方法（特邀章节）》牛津大学出版社。

原田俊郎: "アルキニルメタルのβ炭素上における求核反応性と炭素骨格構築反応への利用"有機合成化学協会誌. 59. 101-108 (2001)

Toshiro Harada：“炔基金属 β 碳上的亲核反应性及其在碳骨架构建反应中的应用”有机合成化学学会杂志 59. 101-108 (2001)。

Toshiro Harada: "Nucleophilic Reactivity of Alkynylmetals at the β-Position : Application to the Construction of Carbon Frameworks"J.Syn.Org.Chem., Japan. 59. 101-108 (2000)

Toshiro Harada：“炔基金属在 β 位的亲核反应性：在碳框架构建中的应用”J.Syn.Org.Chem.，日本 59. 101-108 (2000)。

Toshiro Harada: "Novel Homologation Reaction of Arylzincates Bearing a Leaving Group at the Ortho and Meta Positions"J.Org.Chem.. 64. 8210-8213 (1999)

Toshiro Harada：“邻位和间位带有离去基团的芳基锌酸盐的新型同系反应”J.Org.Chem.. 64. 8210-8213 (1999)

Toshiro Harada: "Tandem Cyclization of Alkynylmetals Bearing Remote Leaving Group via Cycloalkylidene Carbenes"Organic Letters. 2. 1855-1857 (2000)

Toshiro Harada：“通过亚环烷基卡宾对带有远程离去基团的炔基金属进行串联环化”有机快报。