Direct Alkene and Alkyne Borylation with Borenium Cations

用硼阳离子直接进行烯烃和炔烃硼化

• 批准号: EP/J000973/1
• 负责人: Michael Ingleson
• 金额: $ 46.18万
• 依托单位: University of Manchester
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2012
• 资助国家: 英国
• 起止时间: 2012 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FJ000973%2F1
• 关键词: Direct; Alkene; Alkyne; Borylation; Borenium

Organic molecules containing boron substituents are widespread intermediates in the synthesis of new molecules for drug discovery, agrochemicals and organic electronics. This ubiquity arises from their high efficacy in a range of functional group transformations, particularly those involving the formation of new C-X bonds (X = carbon, nitrogen, oxygen). The combination of this efficacy with the stability and ease of handling of common boron containing compounds explains their extraordinary popularity amongst synthetic chemists. However, the installation of a boron group onto an organic molecule (termed borylation) has historically proceeded by inefficient processes, often requiring numerous steps, undesirable intermediates, highly reactive reagents and cryogenic conditions. A new generation of borylation methodologies has improved this situation somewhat, but these approaches require either halogenated intermediates, expensive transition metal catalysts or cannot be applied to certain important families of compounds. Thus the development of fundamentally new borylation methodologies for unsaturated organic molecules, e.g., alkenes and alkynes that proceeds in one step without requiring toxic precious metal catalysts and cryogenic conditions would be extremely valuable.We have recently shown that cyclic organic molecules (arenes) can be borylated using three coordinate cationic boron compounds, termed borenium cations. This process takes place rapidly and with high selectivity at ambient temperature using inexpensive and readily synthesised borenium cations. Importantly this process occurs in one-step without precious metals and is applicable to classes of compounds other modern methodologies struggle with. This proposal will extend this breakthrough by using borenium cations to borylate a wide range of alkynes and alkenes. These acyclic compounds will react in an analogous manner to arenes allowing for the direct conversion of a C-H bond into a C-B bond facilely generating the valuable borylated organic product. By subtle modification of the borenium cation we will also sequentially add a boron and a hydrogen substituent to an alkene or alkyne (termed hydroboration). Classic hydroboration routes involved the simultaneous addition of B and H which results in a certain product geometry. The borenium cation based process will be a stepwise addition of B and H substituents, enabling a complementary addition geometry to be accessed. This will allow for the inexpensive synthesis of important organic building blocks that have hitherto been inaccessible or required complex multi-step syntheses.Throughout the commercial viability of this research will be ensured by the continual use of inexpensive reagents and by borylating alkenes and alkynes of relevance to the pharmaceutical and organoelectronic industries. The combination of borenium cation with alkenes and alkynes will provide access to a range of important compounds currently either inaccessible or not commercially viable using established methodologies.

含硼取代基的有机分子是药物开发、农用化学品和有机电子等新分子合成中广泛使用的中间体。这种普遍存在源于它们在一系列官能团转化中的高效率，特别是那些涉及形成新的C-X键（X =碳，氮，氧）的官能团。这种功效与稳定性和易于处理普通含硼化合物的结合解释了它们在合成化学家中非常受欢迎的原因。然而，在有机分子上安装硼基团（称为硼基化）历来都是低效的过程，通常需要许多步骤、不需要的中间体、高活性试剂和低温条件。新一代的硼化方法在一定程度上改善了这种情况，但这些方法要么需要卤化中间体，要么需要昂贵的过渡金属催化剂，要么不能应用于某些重要的化合物家族。因此，为不饱和有机分子（例如，烯烃和炔）开发一种全新的硼化方法，而不需要有毒的贵金属催化剂和低温条件，这将是非常有价值的。我们最近表明，环状有机分子（芳烃）可以用三种配位阳离子硼化合物硼化，称为硼阳离子。这一过程在室温下使用廉价和容易合成的硼离子进行，速度快，选择性高。重要的是，这一过程一步完成，不含贵金属，适用于其他现代方法难以处理的化合物类别。该提案将通过使用硼离子来扩展这一突破，以硼化广泛的炔烃和烯烃。这些无环化合物将以类似于芳烃的方式反应，允许将C-H键直接转化为C-B键，从而容易地生成有价值的硼化有机产物。通过对硼离子的细微修饰，我们也将依次在烯烃或炔上添加硼和氢取代基（称为硼氢化）。经典的硼氢化路线涉及B和H的同时加入，从而产生一定的产品几何形状。基于硼离子的过程将是B和H取代基的逐步添加，从而实现互补的添加几何形状。这将使迄今为止难以获得或需要复杂的多步合成的重要有机构建块的廉价合成成为可能。通过持续使用廉价试剂和硼化与制药和有机电子工业相关的烯烃和炔，将确保这项研究的整个商业可行性。硼离子与烯烃和炔的结合将提供一系列重要的化合物的途径，这些化合物目前要么无法获得，要么使用既定的方法在商业上不可行。

项目成果

syn-1,2-carboboration of alkynes with borenium cations.

与硼阳离子的炔烃的Syn-1,2-晶状体。

• DOI: 10.1002/chem.201403614
• 发表时间: 2014-09-26
• 期刊: CHEMISTRY-A EUROPEAN JOURNAL
• 影响因子: 4.3
• 作者: Cade, Ian A.;Ingleson, Michael J.
• 通讯作者: Ingleson, Michael J.

Room temperature ring expansion of N-heterocyclic carbenes and B-B bond cleavage of diboron(4) compounds.

• DOI: 10.1002/chem.201501498
• 发表时间: 2015-06
• 期刊: Chemistry
• 作者: S. Pietsch;Ursula S. D. Paul;I. Cade;M. Ingleson;U. Radius;T. Marder

Haloboration of internal alkynes with boronium and borenium cations as a route to tetrasubstituted alkenes.

用硼和硼阳离子的内藻类的磨蚀性，作为通往四碱烷烃的途径。

• DOI: 10.1002/anie.201302609
• 发表时间: 2013-07-15
• 期刊: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
• 影响因子: 16.6
• 作者: Lawson, James R.;Clark, Ewan R.;Cade, Ian A.;Solomon, Sophia A.;Ingleson, Michael J.
• 通讯作者: Ingleson, Michael J.

Enhancing electron affinity and tuning band gap in donor-acceptor organic semiconductors by benzothiadiazole directed C-H borylation.

• DOI: 10.1039/c5sc01800e
• 发表时间: 2015-09-01
• 期刊: Chemical science
• 影响因子: 8.4
• 作者: Crossley DL;Cade IA;Clark ER;Escande A;Humphries MJ;King SM;Vitorica-Yrezabal I;Ingleson MJ;Turner ML
• 通讯作者: Turner ML

Formation of C(sp 2 )?Boronate Esters by Borylative Cyclization of Alkynes Using BCl 3

使用 BCl 3 通过硼基化炔烃环化形成 C(sp 2 )?硼酸酯

• DOI: 10.1002/ange.201505810
• 发表时间: 2015
• 期刊: Angewandte Chemie
• 作者: Warner A