New Methods for Synthesis via Oxidative Coupling

氧化偶联合成新方法

• 批准号: 8101582
• 负责人: Brenton L. DeBoef
• 金额: $ 32.86万
• 依托单位: UNIVERSITY OF RHODE ISLAND
• 依托单位国家: 美国
• 财政年份: 2011
• 资助国家: 美国
• 起止时间: 2011-06-01 至 2015-05-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/8101582
• 关键词: Alkanes; Amides; Amination; Amines; Area; Benzimidazoles; Biological Factors; Biomimetics; Carbon; Chemicals; Cleaved cell; Complex; Coupled; Coupling; Cyclic Peptides; Derivation procedure; Development; Electrons; Hazardous Waste; Hydrogen; Hydrogen Bonding; Investigation; Iodides; Iodine; Iron; Laboratories; Mediating; Methods; Nitrogen; Organic Synthesis; Palladium; Peptides; Pharmacologic Substance; Phthalimides; Process; Production; Publishing; Reaction; Reagent; Rhode Island; Rhodium; Route; Science; Students; Synthesis Chemistry; Technology; Testing; Training; Universities; Work; base; benzimidazole; catalyst; chemical reaction; novel; process optimization; tool; wasting

DESCRIPTION (provided by applicant): Reactions that form carbon-carbon (C-C) and carbon nitrogen (C-N) bonds via the direct oxidative coupling of two carbon-hydrogen (C-H) or nitrogen-hydrogen (N-H) bonds are valuable tools for the organic synthesis of biologically active molecules. The three proposed projects involve either the synthesis of biaryls via oxidative coupling of two sp2-hybridized C-H bonds or oxidative amination via the direct coupling of an sp2-hybridized C-H with the N-H of phthalimide. Significant preliminary results have been generated for each of the processes. In each case, hypothesis-driven mechanistic investigations are proposed. The accomplishment of the proposed work will provide organic chemists with new paradigms, through which they can envision synthetic routes to complex target molecules. PUBLIC HEALTH RELEVANCE: This proposal describes the development of new chemical reactions that simultaneously cleave two carbon-hydrogen bonds or nitrogen-hydrogen bonds and couple them to form carbon-carbon bonds or carbon-nitrogen bonds. This technology will streamline the synthesis of organic molecules, such as pharmaceuticals, by reducing the number of chemical derivations that are required to form carbon-carbon bonds, as well as reducing the hazardous waste associated with organic synthesis. Additionally, the application of this technology to the synthesis biaryl peptides, an important class of bioactive natural products, is proposed.

描述（由申请人提供）：通过两个碳-氢（C-H）或氮-氢（N-H）键的直接氧化偶联形成碳-碳（C-C）和碳氮（C-N）键的反应是有机合成的宝贵工具。生物活性分子的合成。这三个拟议项目涉及通过两个 sp2 杂化 C-H 键的氧化偶联合成联芳基化合物，或通过 sp2 杂化 C-H 与邻苯二甲酰亚胺的 N-H 直接偶联进行氧化胺化。每个过程都产生了重要的初步结果。在每种情况下，都提出了假设驱动的机制研究。这项工作的完成将为有机化学家提供新的范例，通过这些范例，他们可以设想复杂目标分子的合成路线。 公共健康相关性：该提案描述了新化学反应的发展，该反应同时裂解两个碳-氢键或氮-氢键并将它们偶联以形成碳-碳键或碳-氮键。该技术将通过减少形成碳-碳键所需的化学衍生物的数量以及减少与有机合成相关的危险废物来简化药物等有机分子的合成。此外，还提出将该技术应用于合成二芳基肽（一类重要的生物活性天然产物）。

项目成果

Metal-free intermolecular oxidative C-N bond formation via tandem C-H and N-H bond functionalization.

通过串联 C-H 和 N-H 键功能化形成无金属分子间氧化 C-N 键。

• 发表时间: 2011-12-14
• 影响因子: 15
• 作者: Kantak, Abhishek A;Potavathri, Shathaverdhan;Barham, Rose A;Romano, Kaitlyn M;DeBoef, Brenton
• 通讯作者: DeBoef, Brenton

Intramolecular arylation of benzimidazoles via Pd(II)/Cu(I) catalyzed cross-dehydrogenative coupling.

通过 Pd(II)/Cu(I) 催化的交叉脱氢偶联进行苯并咪唑的分子内芳基化。

• 发表时间: 2014-03-05
• 影响因子: 1.8
• 作者: Pereira, Kyle C;Porter, Ashley L;Deboef, Brenton
• 通讯作者: Deboef, Brenton

Iron-catalyzed arylation of heterocycles via directed C-H bond activation.

通过直接 C-H 键活化，铁催化杂环芳基化。

• 发表时间: 2014-02-07
• 影响因子: 5.2
• 作者: Sirois, John J;Davis, Riley;DeBoef, Brenton
• 通讯作者: DeBoef, Brenton

Regioselective gold-catalyzed oxidative C-N bond formation.

区域选择性金催化氧化 C-N 键形成。

• 发表时间: 2015-01-16
• 影响因子: 5.2
• 作者: Marchetti, Louis;Kantak, Abhishek;Davis, Riley;DeBoef, Brenton
• 通讯作者: DeBoef, Brenton

A Modern Apparatus for Performing Flash Chromatography: An Experiment for the Organic Laboratory.

进行快速色谱分析的现代仪器：有机实验室的实验。

• 发表时间: 2013-03-12
• 影响因子: 3
• 作者: Naumiec, Gregory R;Del Padre, Angela N;Hooper, Matthew M;St Germaine, Alison;Deboef, Brenton
• 通讯作者: Deboef, Brenton