Expanding the Scope of Organobismuth Compounds in Organic Synthesis

扩大有机铋化合物在有机合成中的应用范围

• 批准号: RGPIN-2017-05605
• 负责人: Gagnon, Alexandre
• 金额: $ 1.6万
• 依托单位: Université du Québec à Montréal
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2019
• 资助国家: 加拿大
• 起止时间: 2019-01-01 至 2020-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=678683
• 关键词: Expanding; Scope; Organobismuth; Compounds; Organic

Bismuth is the 83rd element of the Periodic Table. This heavy metal is the last stable atom of group V of the main p block elements, called the pnictogens. Despite its heavy atomic weight, elemental bismuth shows surprisingly low toxicity. In fact, bismuth-derived compounds have been used as antibiotics, radiopaque bone cements, anticancer agents, drugs for the treatment of gastrointestinal disorders and in many other medicinal applications.******Organobismuth compounds, a class of organometallic reagents that contain a C-Bi bond, are subdivided into two main groups: trivalent and pentavalent organobismuthines where the metal is in the +3 and +5 oxidation state, respectively. A wide diversity of geometries have been found for organobismuth compounds depending on the oxidation state of bismuth (+3, +5), its overall charge (-1, 0, +1, +2) and its number of coordinated elements (3, 4, 5, 6). Due to its lone pair, trivalent organobismuthines can act as sigma-donor ligands in transition metal complexes. In addition, even though bismuth has a full electronic shell, organobismuth compounds can also act as Lewis acids by forming hypervalent interactions with ligands. Due to these remarkable and unique properties, organobismuth compounds have found applications in total synthesis, methodology development, polymerization reactions as well as in 'green', organometallic and medicinal chemistry.******Our group reported protocols to prepare functionalized triaryl, trialkyl and tricyclopropylbismuthines. In particular, we developed an efficient strategy for the synthesis of highly functionalized triarylbismuthines that involves direct triple functional group manipulation directly on the organometallic species. These organobismuth compounds were used in a portfolio of copper-catalyzed arylation, alkylation and cyclopropylation reactions as well as in palladium-catalyzed cross-coupling reactions with aryl/heteroaryl and vinyl halides and triflates. These methods, which lead to the construction of C-C, C-N and C-O bonds, operate under mild conditions, show high functional group tolerance and allow the installation of functionalized groups on medicinally relevant scaffolds.******In this research program, we propose to use the unique properties of organobismuth compounds to develop novel reactions that allow the modification of bioorganic compounds, enable new types of reactions, and give access to synthetically challenging molecules. We will also prepare novel organobismuth compounds that have unique electronic, steric and geometric properties, that possess solubilizing groups, that lead to hypervalency and chirality, and that can find applications in catalysis, electrochemistry, material sciences and tectonics. This program is ideally suited for training highly qualified personnel with multidisciplinary skills in the field of catalysis, organic, organometallic and green chemistry.

Bismuth是周期表的第83个元素。这种重金属是主要P块元件V组V组的最后一个稳定原子，称为Pnictogens。尽管重量很大，但元素二晶曲表现出令人惊讶的低毒性。实际上，其经用作抗生素的化合物已被用作抗生素，放射性骨水泥，抗癌药，用于治疗胃肠道疾病的药物以及在许多其他药物应用中。分别+3和+5氧化态。有机抗体化合物的几何形状多种多样，具体取决于鞭毛的氧化状态（+3，+5），其整体电荷（-1、0，+1，+2）及其协调元素的数量（3、4、5、6）。由于其孤独的对，三价有机氨基硫酸盐可以充当过渡金属配合物中的Sigma-Donor配体。此外，即使二木具有完整的电子壳，有机晶化合物也可以通过与配体的高价相互作用来充当刘易斯酸。由于这些显着且独特的特性，有机晶体化合物在总合成，方法论开发，聚合反应以及“绿色”，有机金属和药物化学中发现了应用。特别是，我们开发了一种有效的策略，用于合成高度功能化的三轴氨基曲线，该策略直接在有机金属物种上直接涉及直接的三重功能组操作。这些有机晶体化合物用于铜催化的芳基化，烷基化和环丙基反应以及与芳基/杂芳基和乙烯基卤化物和三叶片的铜催化芳基化，烷基化和环丙基反应。 These methods, which lead to the construction of C-C, C-N and C-O bonds, operate under mild conditions, show high functional group tolerance and allow the installation of functionalized groups on medicinally relevant scaffolds.******In this research program, we propose to use the unique properties of organobismuth compounds to develop novel reactions that allow the modification of bioorganic compounds, enable new types of reactions, and give access to合成具有挑战性的分子。我们还将制备具有独特的电子，空间和几何特性的新型有机晶体化合物，这些化合物具有溶解的群体，可导致过度效能和手性，并且可以在催化，电化学，材料科学和构造中找到应用。该计划非常适合在催化，有机，有机金属和绿色化学领域具有多学科技能的高素质人员培训。