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。硼化合物是化学中使用最广泛的试剂之一，并被用于无数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在合成化学和药物化学中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获得了两项诺贝尔奖（1979年布朗奖和2010年铃木奖）。尽管取得了这些进展，但几乎所有这些化合物都是由硼作为电子受体（亲电试剂）的原料合成的。这是硼在元素周期表中位于第13族顶部的自然结果，并且对可以制造的硼化合物的类型和种类提出了严重的限制。在这个项目中，我们将以我们最近的发现（Nature common . 2017,8,15022）为基础，即硼与电负性较低的第2族元素镁结合的衍生物，很容易通过激活商业上可用的二硼烷的B-B键产生。与绝大多数可用的硼试剂相比，这些化合物中的硼作为一个强有力的电子供体（亲核试剂）反应，提供了允许合成各种新的含硼分子的潜力。在这个项目中，我们将采用多方面的无机/有机合成和计算方法来设计、理解和应用一系列新的和高活性的2族金属硼衍生物，主要是镁和钙。这些后一种元素的吸引力在于它们的毒性可忽略不计，天然丰度高，因而成本低。此外，在这个项目中开发的亲核硼试剂将用于合成大量前所未有的和以前难以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那里获得，并且在合成化学家的储藏室中建立以前无法获得的亲核硼试剂作为现成的试剂。

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

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.

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

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