Catalytic Functionalization of C-H Bonds with Main Group Reagents
主族试剂对 C-H 键的催化官能化
基本信息
- 批准号:8946206
- 负责人:
- 金额:$ 34.92万
- 依托单位:
- 依托单位国家:美国
- 项目类别:
- 财政年份:2015
- 资助国家:美国
- 起止时间:2015-08-15 至 2019-04-30
- 项目状态:已结题
- 来源:
- 关键词:AffectAlcoholsAlkylationAminesAromatic AminesBoranesCarbonComplexCyclic EthersCyclopropanesDataDevelopmentElectronicsEthersFelis catusGenerationsGoalsGrantHealthHumanHydrocarbonsHydrogen BondingIndividualInterceptIridiumKetonesLigandsMetalsMethodsN.I.H. Research SupportNatureNitrogenPharmaceutical ChemistryPharmacologic SubstancePhenanthrolinesPhosphinesPhosphorusProcessPropertyPublishingReactionReagentRelative (related person)ResearchRestRhodiumScienceSilanesSiliconSiloxanesSiteStructureSystemTimeTransition Elementsbasecatalystcyclopropanedesigndrug discoveryfunctional groupimprovedinnovationpublic health relevancesilanesuccessunpublished works
项目摘要
DESCRIPTION (provided by applicant): Methods for the catalytic functionalization of C-H bonds are widely considered to possess the potential to revolutionize the synthesis of complex molecules, but the realization of this potential requires the selective functionalization of a singe C-H bond in compounds containing many other C-H bonds and functional groups that are typically more reactive than the C-H bond. The PI is developing an unusual strategy for the functionalization of C-H bonds involving the reactions of boranes and, more recently, of silanes with aryl, heteroaryl, and alkyl C-H bonds. The products from these reactions are valuable synthetic intermediates that can be converted to diverse final products containing new C-C, C-N, C-O, and C-S bonds. The fundamental innovation underlying the C-H bond functionalization in this proposal is the higher reactivity of complexes containing covalent transition metal-main group bonds toward C-H bond functionalization than those containing typical organometallic ligands. During the past several years, the PI's group has discovered a new class of catalyst for the silylation of aryl C-H bonds; silylmetal complexes that are catalytically competent and react with arenes to form arylsilanes; iridium-catalyzed borylations of aliphatic C-H bonds of cyclopropanes, amines and cyclic ethers; borylations of secondary alkyl and benzyl C-H bonds directed by alcohols and amines; a catalyst for broadly applicable borylations of heteroarenes; and one-pot combinations of borylation and subsequent functionalization to create sterically controlled functionalizations of arenes, alkylations of arenes, and mild access to unstable arylboronate intermediates. The proposed research will build upon these studies and additional preliminary data. The PI's group will prepare new ligand structures that enable metal-catalyzed borylations of primary C-H bonds with limiting substrate, increase the reactivity of the catalysts toward basic heteroarenes, and create practical methods for the silylation of functionalized arenes. In addition, they will use these catalysts to achieve directed borylations and silylations of alkyl C-H bonds and methods for the generation and characterization of intermediates in the iridium-catalyzed borylations and silylations. To achieve these goals, seven major aims are proposed: 1) to design new ligands for the borylation and silylation of aryl and alkyl C-H bonds by iridium and rhodium catalysts; 2) To discover new borylations of aliphatic C-H bonds enabled by the ligands of Aim 1; 3) To gain a mechanistic understanding of the relationships between iridium catalyst structure and activity for C-H borylation; 4) To broaden the scope of directed silylations of aliphatic C-H Bonds; 5) To create intermolecular silylations of aromatic C-H bonds that occur with remote steric effects and high functional group compatibility; 6) To reveal the mechanism of these intermolecular silylations of arenes, and 7) To develop new functionalizations of the main group products of the C-H bond functionalizations.
项目成果
期刊论文数量(0)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
数据更新时间:{{ journalArticles.updateTime }}
{{
item.title }}
{{ item.translation_title }}
- DOI:
{{ item.doi }} - 发表时间:
{{ item.publish_year }} - 期刊:
- 影响因子:{{ item.factor }}
- 作者:
{{ item.authors }} - 通讯作者:
{{ item.author }}
数据更新时间:{{ journalArticles.updateTime }}
{{ item.title }}
- 作者:
{{ item.author }}
数据更新时间:{{ monograph.updateTime }}
{{ item.title }}
- 作者:
{{ item.author }}
数据更新时间:{{ sciAawards.updateTime }}
{{ item.title }}
- 作者:
{{ item.author }}
数据更新时间:{{ conferencePapers.updateTime }}
{{ item.title }}
- 作者:
{{ item.author }}
数据更新时间:{{ patent.updateTime }}
John F Hartwig其他文献
John F Hartwig的其他文献
{{
item.title }}
{{ item.translation_title }}
- DOI:
{{ item.doi }} - 发表时间:
{{ item.publish_year }} - 期刊:
- 影响因子:{{ item.factor }}
- 作者:
{{ item.authors }} - 通讯作者:
{{ item.author }}
{{ truncateString('John F Hartwig', 18)}}的其他基金
Discovery and Development of Organic Reactions Catalyzed by Transition Metals Valuable for Medicinal Chemistry
具有药物化学价值的过渡金属催化有机反应的发现和发展
- 批准号:
10316182 - 财政年份:2019
- 资助金额:
$ 34.92万 - 项目类别:
Discovery and Development of Organic Reactions Catalyzed by Transition Metals Valuable for Medicinal Chemistry
具有药物化学价值的过渡金属催化有机反应的发现和发展
- 批准号:
10728381 - 财政年份:2019
- 资助金额:
$ 34.92万 - 项目类别:
Discovery and Development of Organic Reactions Catalyzed by Transition Metals Valuable for Medicinal Chemistry
具有药物化学价值的过渡金属催化有机反应的发现和发展
- 批准号:
10623699 - 财政年份:2019
- 资助金额:
$ 34.92万 - 项目类别:
Discovery and Development of Organic Reactions Catalyzed by Transition Metals Valuable for Medicinal Chemistry
具有药物化学价值的过渡金属催化有机反应的发现和发展
- 批准号:
10387536 - 财政年份:2019
- 资助金额:
$ 34.92万 - 项目类别:
Discovery and Development of Organic Reactions Catalyzed by Transition Metals Valuable for Medicinal Chemistry
具有药物化学价值的过渡金属催化有机反应的发现和发展
- 批准号:
10830116 - 财政年份:2019
- 资助金额:
$ 34.92万 - 项目类别:
Discovery and Development of Organic Reactions Catalyzed by Transition Metals Valuable for Medicinal Chemistry
具有药物化学价值的过渡金属催化有机反应的发现和发展
- 批准号:
10079494 - 财政年份:2019
- 资助金额:
$ 34.92万 - 项目类别:
Discovery and Development of Organic Reactions Catalyzed by Transition Metals Valuable for Medicinal Chemistry
具有药物化学价值的过渡金属催化有机反应的发现和发展
- 批准号:
10543417 - 财政年份:2019
- 资助金额:
$ 34.92万 - 项目类别:
Discovery and Development of Organic Reactions Catalyzed by Transition Metals Valuable for Medicinal Chemistry
具有药物化学价值的过渡金属催化有机反应的发现和发展
- 批准号:
10214396 - 财政年份:2019
- 资助金额:
$ 34.92万 - 项目类别:
RATIONAL DESIGN OF CATALYSTS FOR C-C BOND FORMATION
C-C 键形成催化剂的合理设计
- 批准号:
6519916 - 财政年份:1999
- 资助金额:
$ 34.92万 - 项目类别:
RATIONAL DESIGN OF CATALYSTS FOR C-C BOND FORMATION
C-C 键形成催化剂的合理设计
- 批准号:
2835567 - 财政年份:1999
- 资助金额:
$ 34.92万 - 项目类别:
相似海外基金
Collaborative Research: Overlooked Oxidation of Aqueous Alcohols: Kinetics, Mechanism, and Relevance to Water Reuse
合作研究:被忽视的水醇氧化:动力学、机制以及与水回用的相关性
- 批准号:
2304861 - 财政年份:2023
- 资助金额:
$ 34.92万 - 项目类别:
Continuing Grant
STTR Phase I: Development of Modular Reactors to Convert Methane to Alcohols at Low Temperatures
STTR 第一阶段:开发在低温下将甲烷转化为醇的模块化反应器
- 批准号:
2151256 - 财政年份:2023
- 资助金额:
$ 34.92万 - 项目类别:
Standard Grant
Development of amine-dehydrogenase and lyase biocatalysts for the sustainable manufacturing of unnatural chiral amino acids and amino alcohols
开发胺脱氢酶和裂解酶生物催化剂,用于可持续生产非天然手性氨基酸和氨基醇
- 批准号:
2870226 - 财政年份:2023
- 资助金额:
$ 34.92万 - 项目类别:
Studentship
Collaborative Research: Overlooked Oxidation of Aqueous Alcohols: Kinetics, Mechanism, and Relevance to Water Reuse
合作研究:被忽视的水醇氧化:动力学、机制以及与水回用的相关性
- 批准号:
2304860 - 财政年份:2023
- 资助金额:
$ 34.92万 - 项目类别:
Continuing Grant
Postdoctoral Fellowship: MPS-Ascend: Development of Selective Reaction Schemes for Photoactivation of Alcohols
博士后奖学金:MPS-Ascend:醇光活化选择性反应方案的开发
- 批准号:
2316541 - 财政年份:2023
- 资助金额:
$ 34.92万 - 项目类别:
Fellowship Award
Development of phosphorylation of alcohols in protein based on the structural modification of phosphoenolpyruvate
基于磷酸烯醇丙酮酸结构修饰的蛋白质醇磷酸化研究进展
- 批准号:
22KJ1152 - 财政年份:2023
- 资助金额:
$ 34.92万 - 项目类别:
Grant-in-Aid for JSPS Fellows
Nickel Cross-Coupling Cascades with α-Heteroatom Radicals to Prepare Sterically Hindered Alcohols and Amines
镍与α-杂原子自由基交叉偶联级联制备位阻醇和胺
- 批准号:
10604535 - 财政年份:2023
- 资助金额:
$ 34.92万 - 项目类别:
Towards a better understanding of the effect of the pentafluorosulfanyl group on the lipophilicity and acid/base properties of alcohols and amines
更好地了解五氟硫基对醇和胺的亲脂性和酸/碱性质的影响
- 批准号:
571856-2021 - 财政年份:2022
- 资助金额:
$ 34.92万 - 项目类别:
Alliance Grants
Pd-Catalyzed C(sp3)-H Functionalizations Directed by Free Alcohols and Boc-Protected Amines
由游离醇和 Boc 保护的胺引导的 Pd 催化 C(sp3)-H 官能化
- 批准号:
10606508 - 财政年份:2022
- 资助金额:
$ 34.92万 - 项目类别:
Facile One-Pot Reductive Deoxygenations of Alcohols and Carboxylic Acids Using Sulfuryl Fluoride
使用硫酰氟轻松进行醇和羧酸的一锅还原脱氧
- 批准号:
546996-2020 - 财政年份:2022
- 资助金额:
$ 34.92万 - 项目类别:
Alexander Graham Bell Canada Graduate Scholarships - Doctoral