1,1-Carboboration of Alkynes - Development of an Unusual Reaction

炔烃的 1,1-碳硼化 - 异常反应的发展

• 批准号: 183729294
• 负责人: Professor Dr. Gerhard Erker
• 金额: --
• 依托单位: Organisch-Chemisches Institut
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2010
• 资助国家: 德国
• 起止时间: 2009-12-31 至 2017-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/183729294?language=en
• 关键词: Carboboration; Alkynes; Development; Unusual; Reaction

In our preliminary work we could show that the utilization of strongly Lewis-acidic boranes with pentafluorophenyl substituents enormously enhanced the rates and scope of the 1,1-carboboration reaction. In this situation even die migrating aptitude of hydrogen is sufficient to convert simple terminal alkynes into their respective substituted alkenyl boranes. P-, S- and B-migration takes place under these conditions and one can even carry out 1,1-carboboration reactions of internal alkynes by means of C-C bond activation. These results shall now be used to achieve a substantial expansion of the 1,1 carboboration reaction scheme. We want to prepare extended pi-systems in this way. Subsequent oxidative deborylation will then lead to conjugated enones. Cyclic variants shall be prepared starting from vicinal diacetylenes. We propose the cyclization of unsaturated vicinal diacetylenes to give benzannulated products. One focus of the project will be the development of the chemistry of thiophenes, phospholes and boroles which should become available conveniently by 1,1-carboboration sequences starting from the respective readily prepared doubly acetylide substituted heteroatom containing precursors. Eventually, we have planned to develop simple syntheses to symmetrical and unsymmetrical S-, P- and B-containing cyclic five-membered pi-systems by the 1,1-carboboration scheme, which might potentially be of interest in organic materials science.

在我们的初步工作中，我们可以表明，利用强路易斯酸硼烷与五氟苯基取代基大大提高了1，1-碳硼化反应的速度和范围。在这种情况下，甚至氢的迁移能力也足以将简单的末端炔转化为它们各自的取代烯基硼烷。在这些条件下发生P-、S-和B-迁移，甚至可以通过C-C键活化进行内炔的1，1-碳硼化反应。这些结果现在将用于实现1，1碳硼化反应方案的实质性扩展。我们想以这种方式准备扩展的π系统。随后的氧化脱硼将导致共轭烯酮。环状变体应从邻位二乙炔开始制备。我们提出了不饱和邻位二乙炔的环化反应，得到苯并环化产物。该项目的一个重点将是噻吩，磷杂环戊二烯和硼杂环戊二烯的化学发展，这些化合物应该从各自容易制备的双乙炔基取代的含杂原子的前体开始，通过1，1-碳硼化序列方便地获得。最后，我们计划通过1，1-碳硼化方案来开发简单的合成对称和不对称的含S-、P-和B-的环状五元π-体系，这可能在有机材料科学中具有潜在的兴趣。

项目成果

Preparation of dithienylphospholes by 1,1-carboboration.

• DOI: 10.1002/chem.201403102
• 发表时间: 2014-09
• 期刊: Chemistry
• 作者: Juri Möbus;A. Galstyan;Andreas Feldmann;C. Daniliuc;R. Fröhlich;C. Strassert;G. Kehr;G. Erker

Reactions of Boroles Formed by 1,1-Carboboration

• DOI: 10.1021/om501085j
• 发表时间: 2015-01-12
• 期刊: ORGANOMETALLICS
• 影响因子: 2.8
• 作者: Ge, Fang;Kehr, Gerald;Erker, Gerhard
• 通讯作者: Erker, Gerhard