Nucleophilic Alkaline Earth Boryls: From Conception and Theory to Application

亲核碱土硼基化合物：从概念、理论到应用

• 批准号: EP/R020752/1
• 负责人: Michael Hill
• 金额: $ 162.74万
• 依托单位: University of Bath
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2018
• 资助国家: 英国
• 起止时间: 2018 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FR020752%2F1
• 关键词: Nucleophilic; Alkaline; Earth; Boryls; Conception

Some of the greatest benefits to human health and well-being have been provided by modern methods of chemical synthesis. Boron compounds provide some of the most widely used reagents in chemistry and are employed in myriad syntheses of pharmaceutical and other high value molecules (e.g. with uses in electronic materials and chemical sensing). Organoborane, boronate ester and boronic acid derivatives, thus, provide some of the most practically useful intermediates in synthetic and medicinal chemistry, to the extent that the application of boron in organic synthesis has been recognised by the award of two Nobel prizes (Brown in 1979 and Suzuki in 2010). Despite these advances, almost all of these compounds are synthesised from starting materials in which boron acts as an electron acceptor (electrophile). This is a natural consequence of boron's position at the top of group 13 in the periodic table and presents a severe limitation to the types and variety of boron compounds that can be made. In this project we will build on our recent discovery (Nature Commun. 2017, 8, 15022) that derivatives in which boron is bonded to a less electronegative group 2 element, magnesium, are easily generated by activation of the B-B bonds of commercially available diboranes. In contrast to the vast majority of available boron reagents, the boron in these compounds reacts as a potent electron donor (nucleophile), providing the potential to allow the synthesis of a wide variety of new boron-containing molecules. In this project, we will apply a multifaceted inorganic/organic synthetic and computational approach to devise, understand and apply a wide array of new and highly reactive boron derivatives of the group 2 metals, primarily magnesium and calcium. The attractiveness of these latter elements is underscored by their negligible toxicity, high natural abundance and resultant low cost. Furthermore, the boron nucleophiles developed in this project will be used in the synthesis of a plethora of unprecedented and previously inaccessible organic and inorganic boron-containing compounds. Our ultimate objective is to ensure that these reagents are available from commercial chemical suppliers and nothing short of establishing previously inaccessible boron nucleophiles as off-the-shelf reagents in the synthetic chemist's larder.

现代化学合成方法为人类健康和福祉带来了一些最大的好处。硼化合物提供了化学中一些最广泛使用的试剂，并用于多种药物和其他高价值分子的合成（例如用于电子材料和化学传感）。因此，有机硼烷、硼酸酯和硼酸衍生物为合成和药物化学提供了一些最实用的中间体，以至于硼在有机合成中的应用已获得两项诺贝尔奖的认可（布朗于1979年和铃木于2010年）。尽管取得了这些进步，但几乎所有这些化合物都是由硼作为电子受体（亲电子试剂）的起始材料合成的。这是硼在元素周期表中第 13 族顶部位置的自然结果，并且对可制造的硼化合物的类型和种类提出了严格的限制。在这个项目中，我们将基于我们最近的发现（Nature Commun. 2017, 8, 15022），即通过激活市售乙硼烷的 B-B 键，可以轻松生成硼与电负性较小的第 2 族元素镁键合的衍生物。与绝大多数可用的硼试剂相比，这些化合物中的硼作为有效的电子供体（亲核试剂）发生反应，为合成各种新型含硼分子提供了潜力。在这个项目中，我们将应用多方面的无机/有机合成和计算方法来设计、理解和应用第 2 族金属（主要是镁和钙）的各种新型高反应性硼衍生物。后面这些元素的吸引力在于其毒性可忽略不计、自然丰度高且成本低。此外，该项目中开发的硼亲核试剂将用于合成大量前所未有的、以前无法获得的有机和无机含硼化合物。我们的最终目标是确保这些试剂可以从商业化学品供应商处获得，并且无异于将以前无法获得的硼亲核试剂建立为合成化学家储藏室中的现成试剂。

项目成果

Carbon-Carbon Bond Forming Reactions Promoted by Aluminyl and Alumoxane Anions: Introducing the Ethenetetraolate Ligand

铝基和铝氧烷阴离子促进的碳-碳键形成反应：引入乙烯四醇盐配体

• DOI: 10.1002/ange.202005301
• 发表时间: 2020
• 期刊: Angewandte Chemie
• 作者: Anker M

Potassium Aluminyl Promoted Carbonylation of Ethene

铝基钾促进乙烯羰基化

• DOI: 10.1002/ange.202117396
• 发表时间: 2022
• 期刊: Angewandte Chemie
• 作者: Evans M

Photocatalytic Hydroaminoalkylation of Styrenes with Unprotected Primary Alkylamines.

• DOI: 10.1021/jacs.1c07401
• 发表时间: 2021-10-06
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Askey HE;Grayson JD;Tibbetts JD;Turner-Dore JC;Holmes JM;Kociok-Kohn G;Wrigley GL;Cresswell AJ
• 通讯作者: Cresswell AJ

Potassium Aluminyl Promoted Carbonylation of Ethene.

• DOI: 10.1002/anie.202117396
• 发表时间: 2022-04-11
• 期刊: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
• 影响因子: 16.6
• 作者: Evans, Matthew J.;Neale, Samuel E.;Anker, Mathew D.;McMullin, Claire L.;Coles, Martyn P.
• 通讯作者: Coles, Martyn P.

Decarboxylative, Radical C-C Bond Formation with Alkyl or Aryl Carboxylic Acids: Recent Advances

烷基或芳基羧酸脱羧、自由基 C-C 键形成：最新进展

• DOI: 10.1055/a-2081-1830
• 发表时间: 2023
• 期刊: Synthesis
• 作者: Cresswell A