Tandem Carbon Carbon Bond Forming Reaction via Zincate Carbenid

通过锌酸盐卡贝尼德进行串联碳碳键形成反应

• 批准号: 02650626
• 负责人: HARADA Toshiro
• 金额: $ 1.02万
• 依托单位: Kyoto Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02650626/
• 关键词: Carbenoid; Zincate; Halogen; metal; exchange; Coupling Reaction; Palladium Catalyst

The electrophilic character of carbenoids as a-metallated carbocation equivalents has not been fully demonstrated in contrast to their widely studied nucleophilic nature. In the present study, we disclosed that lithium(1bromoalkenyl)(dialkyl)zincate and lithium(1-bromocyclopropyl)(dialkyl)-zincate which can be generated by a Br/Zn exchange reaction of the corresponding gem-dibromo compounds undergo a facile intramolecular alkylation reaction to give alkenyl- and cyclopropylzinc species. Since the resulting organozinc intermediates have potential of undergoing further C-C bond formation, the reaction was extended to the tandem substitution reaction of gem-dibromo compounds via Pd(O)catalyzed arylation, acylation and alkenylation reaction.

作为α-金属化碳阳离子等价物的类卡宾的亲电特性与其广泛研究的亲核性质相比尚未得到充分证明。在本研究中，我们发现，锂（1溴烯基）（二烷基）锌酸盐和锂（1-溴环丙基）（二烷基）锌酸盐，可以通过相应的偕-二溴化合物的溴/锌交换反应，进行一个简单的分子内烷基化反应，得到烯基-和环丙基锌物种。由于所得有机锌中间体具有进一步形成C-C键的潜力，该反应扩展到偕二溴化合物通过Pd（O）催化的芳基化、酰化和烯基化反应的串联取代反应。

项目成果

Novel Method for Generation of Secondary Organozinc Reagent :"Application to Tandem Carbon-Carbon Bond Formation Reaction of 1, 1-Dibromoalkane" Tetrahedron Lett. 32. 1573-1576 (1991)

生成二次有机锌试剂的新方法：“在1, 1-二溴烷烃串联碳-碳键形成反应中的应用”四面体莱特。

Toshiro Harada: "Novel Method for Generation of Secondary Oranozinc Reagent:Application to Tandem CarbonーCarbon Bond Formation Reaction of 1,1ーDibromoalkane" Tetrahedron Letters. 32. 1573-1576 (1991)

Toshiro Harada：“生成二级有机锌试剂的新方法：在 1,1-二溴烷烃串联碳-碳键形成反应中的应用”四面体快报 32。 1573-1576 (1991)

Toshiro Harada: "Novel Method for Generation of Secondary Oranozinc Reagent: Application to Tandem Carbon-Carbon Bond Formation Reaction of 1,1-Dibromoalkane" Tetrahedron Letters. 32. 1573-1576 (1991)

Toshiro Harada：“生成二级有机锌试剂的新方法：在 1,1-二溴烷烃串联碳-碳键形成反应中的应用”四面体字母。

Toshiro Harada: "Novel Method for Generation of Secondary Oranozinc Reagent:Application to Tandem CarbonーCarbon Bond Formation Reaction of 1,1ーDibromoalkane" Tetrahedron Letters. 32. (1991)

Toshiro Harada：“生成二级有机锌试剂的新方法：在1,1-二溴烷烃串联碳-碳键形成反应中的应用”四面体快报32。（1991）