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）键的反应是用于生物活性分子的有机合成的有价值的工具。这三个项目涉及通过两个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直接偶联的氧化胺化。每个进程都取得了重要的初步成果。在每种情况下，假设驱动的机制调查提出。这项工作的完成将为有机化学家提供新的范式，通过这些范式，他们可以设想复杂目标分子的合成路线。 公共卫生相关性：该提案描述了新的化学反应的发展，该反应同时裂解两个碳-氢键或氮-氢键，并将它们偶联形成碳-碳键或碳-氮键。这项技术将简化有机分子的合成，如药物，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。此外，还提出了该技术在合成一类重要的生物活性天然产物联芳肽中的应用。

项目成果

Transition-metal free umpolung carbon-nitrogen vs. carbon-chlorine bond formation.

无过渡金属的极化碳-氮与碳-氯键的形成。

• DOI: 10.1016/j.tetlet.2015.08.053
• 发表时间: 2015
• 期刊: Tetrahedron letters
• 影响因子: 1.8
• 作者: Sirois,JohnJ;DeBoef,Brenton
• 通讯作者: DeBoef,Brenton

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

• DOI: 10.1016/j.tetlet.2014.01.103
• 发表时间: 2014-03-05
• 期刊: Tetrahedron letters
• 影响因子: 1.8
• 作者: Pereira KC;Porter AL;Deboef B
• 通讯作者: Deboef B

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。

• DOI: 10.1021/ed300360f
• 发表时间: 2013
• 期刊: Journal of chemical education
• 影响因子: 3
• 作者: Naumiec,GregoryR;DelPadre,AngelaN;Hooper,MatthewM;StGermaine,Alison;Deboef,Brenton
• 通讯作者: Deboef,Brenton

Insight into the palladium catalyzed oxidative arylation of benzofuran: Heteropoly acid oxidants evoke a Pd(II)/Pd(IV) mechanism.

• DOI: 10.1016/j.tet.2013.02.061
• 发表时间: 2013-06-01
• 期刊: TETRAHEDRON
• 影响因子: 2.1
• 作者: Pereira, Kyle C.;Porter, Ashley L.;Potavathri, Shathaverdhan;LeBris, Alexis P.;DeBoef, Brenton
• 通讯作者: DeBoef, Brenton

Regioselective C-H bond amination by aminoiodanes.

• DOI: 10.1039/c4cc10246k
• 发表时间: 2015-02-28
• 期刊: Chemical communications (Cambridge, England)
• 作者: Kantak AA;Marchetti L;DeBoef B
• 通讯作者: DeBoef B