Novel Reagents and Catalysts for Organic Synthesis

用于有机合成的新型试剂和催化剂

• 批准号: 10663272
• 负责人: Shih-Yuan Liu
• 金额: $ 32.87万
• 依托单位: BOSTON COLLEGE
• 依托单位国家: 美国
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-09-15 至 2024-07-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/10663272
• 关键词: 1,3-Butadiene; Affect; Amino Acids; Biochemistry; Biological Process; Biology; Biomedical Research; Boron; Butane; Carbon; Categories; Chemicals; Chemistry; Complex; Coupling; Development; Exhibits; Family; Generations; Goals; Indoles; Investigation; Knowledge; Laboratories; Ligands; Metals; Methods; Nitrogen; Organic Chemicals; Organic Chemistry; Organic Synthesis; Oxidation-Reduction; Phosphines; Positioning Attribute; Preparation; Proteins; Reaction; Reagent; Research; Research Methodology; Shapes; Signal Transduction; Structure; Synthesis Chemistry; Technology; Transition Elements; Translations; Tryptophan; Work; absorption; catalyst; density; design; electronic structure; novel; pressure; programs; tool

The generation of chemical space and its translation into new functions is one of the main goals of synthetic chemistry. The BN/CC isosterism (i.e., replacement of a carbon-carbon bond with a boron-nitrogen bond) has emerged as a viable strategy to increase the chemical space of compounds relevant to biomedical research. This proposal describes a program geared toward developing BN isosteres of arenes as useful building blocks, reagents, and catalysts for synthetic organic chemistry and chemical biology applications. Specifically, we seek to: 1) establish azaborines as four-carbon (4C) + 1 nitrogen (1N) + 1 boron (1B) synthon for synthetic applications that exploit the preinstalled functional density of an azaborine, i.e., a nitrogen atom, a boron atom, and a 1,3-butadiene unit to efficiently produce new aminoborylated compounds for diversity-oriented synthesis. 2) establish azaborines as a new family of ligands that can engage in distinct coordination modes with transition metals to affect new reactivity and selectivity in metal-catalyzed transformations. 3) utilize BN-indole and its corresponding amino acid BN-tryptophan to create novel BN-alloproteins and to develop a novel bioconjugation platform that is rapid, catalyst-free, chemoselective, and orthogonal to existing bioconjugation methods. Completion of the proposed aims will yield new fundamental knowledge related to boron in the context of synthetic organic and biological chemistry. It will generate new synthetic methods and research tools for the investigation of biological processes and inspire the design and development of new boron-containing molecules for biomedical applications.

化学空间的生成及其转化为新功能是合成化学的主要目标之一。 BN/CC 电子等排（即用硼-氮键取代碳-碳键）已成为增加生物医学研究相关化合物的化学空间的可行策略。该提案描述了一项旨在开发芳烃的 BN 等排体作为合成有机化学和化学生物学应用的有用构建块、试剂和催化剂的计划。 具体来说，我们力求： 1) 将氮硼烷建立为四碳 (4C) + 1 个氮 (1N) + 1 个硼 (1B) 合成子，用于利用氮硼烷的预装功能密度（即一个氮原子、一个硼原子和一个 1）的合成应用。 ,3-丁二烯单元可有效生产用于多样性合成的新型氨基硼化化合物。 2）建立氮杂硼烷作为一个新的配体家族，它可以与过渡金属形成不同的配位模式，从而影响金属催化转化中的新反应性和选择性。 3）利用BN-吲哚及其相应的氨基酸BN-色氨酸来创建新型BN-同种蛋白，并开发一种快速、无催化剂、化学选择性且与现有生物结合方法正交的新型生物结合平台。 完成拟议目标将在合成有机和生物化学背景下产生与硼相关的新基础知识。它将产生用于生物过程研究的新合成方法和研究工具，并激发用于生物医学应用的新型含硼分子的设计和开发。

项目成果

C-Boron Enolates Enable Palladium Catalyzed Carboboration of Internal 1,3-Enynes.

• DOI: 10.1002/anie.202108534
• 发表时间: 2021-09-20
• 期刊: Angewandte Chemie (International ed. in English)
• 作者: Wang Z;Wu J;Lamine W;Li B;Sotiropoulos JM;Chrostowska A;Miqueu K;Liu SY
• 通讯作者: Liu SY

The aromatic Claisen rearrangement of a 1,2-azaborine

1,2-氮杂硼烷的芳香族克莱森重排

• DOI: 10.1039/d2ob02186b
• 发表时间: 2023
• 期刊: Organic & Biomolecular Chemistry
• 影响因子: 3.2
• 作者: Robichaud, Hannah M.;Ishibashi, Jacob S.;Ozaki, Tomoya;Lamine, Walid;Miqueu, Karinne;Liu, Shih-Yuan
• 通讯作者: Liu, Shih-Yuan

The Versatile Reaction Chemistry of an Alpha-Boryl Diazo Compound.

• DOI: 10.1021/jacs.1c06112
• 发表时间: 2021-09-08
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Liu, Yao;Puig de la Bellacasa, Raimon;Li, Bo;Cuenca, Ana Belen;Liu, Shih-Yuan
• 通讯作者: Liu, Shih-Yuan