Mechanistic Studies at the Frontiers of Catalysis
催化前沿的机理研究
基本信息
- 批准号:10597145
- 负责人:
- 金额:$ 39.05万
- 依托单位:
- 依托单位国家:美国
- 项目类别:
- 财政年份:2022
- 资助国家:美国
- 起止时间:2022-04-01 至 2027-03-31
- 项目状态:未结题
- 来源:
- 关键词:AddressAreaCarbonCatalysisChemistryCouplingEnvironmentFundingGoalsHydrogen BondingIsotopesKineticsLigandsMedicineMetalsMethodologyMethodsMinorModernizationNickelOrganic SynthesisPalladiumPathway interactionsPharmaceutical ChemistryReactionResearchResolutionTimeUnited States National Institutes of HealthVisiondesignforgingfrontierimprovedinsightnovelprogramsrational designtool
项目摘要
Project Summary: Our research program investigates reaction mechanisms in asymmetric
organocatalysis and palladium catalyzed cross-coupling reactions. We utilize 13C and 2H kinetic isotope
effects (KIEs) in combination with theoretical calculations as design tools to evaluate fine details of the
transition state (TS) of the rate-determining step (RDS) under unmodified reaction conditions. Our
studies in the area of asymmetric organocatalysis (2013-present) have resolved long-standing debates,
uncovered novel mechanistic pathways, and probed origins of enantioselectivity in a wide variety of
reaction types. In 2018, NIH funding enabled us to expand our research program to the study of
palladium catalyzed cross-coupling reactions – an area of catalysis that is central to medicinal
chemistry. We have discovered that the magnitude of 13C KIE is highly sensitive to minor changes in
the carbon-palladium distance at the TS of the RDS – allowing us to distinguish between competing
pathways and probe the ligand environment at the metal center, all under catalytic conditions. Finally,
we have developed a novel methodology that utilizes symmetric reactants to obtain this information at a
fraction of the time and effort of traditional KIE approaches.
This MIRA proposal seeks to further expand our research program to include new modes of
catalysis at the frontier of modern-day organic synthesis: (a) palladium catalyzed C-H bond-activation
and functionalization, and (b) nickel metallophotoredox catalysis. Over the next five years, our goal is to
establish our combined experimental and theoretical approach as the state-of-the-art to gain atomistic
understanding of the mechanistic underpinnings of these reactions. We chose these two areas to
expand our research program for two reasons – (a) new reaction discovery has far outpaced
mechanistic understanding of these reactions, and (b) our discoveries in palladium catalyzed cross-
coupling chemistry strongly indicate that our approach is ideally suited to resolve key mechanistic
questions in these contemporary areas of catalysis.
The overall vision of our research program is to develop probes that can rapidly evaluate the
mechanism of catalytic reactions. We seek to change the paradigm that rigorous mechanistic
understanding follows new reaction discovery. We envision that the high-resolution mechanistic insight
that is delivered by our studies will inspire the discovery of new and more robust catalytic methods that
will enable organic synthesis.
项目总结:我们的研究项目是研究不对称的反应机理
有机催化和钯催化的交叉偶联反应。我们利用~(13)C和~2H动力学同位素
效果(Kie)与理论计算相结合作为设计工具来评估
在未改变的反应条件下,速率决定步骤(RDS)的过渡态(TS)。我们的
不对称有机催化领域的研究(2013年至今)解决了长期存在的争论,
发现了新的机制途径,并探索了各种不同的对映选择性的起源
反应类型。2018年,NIH的资助使我们能够将我们的研究计划扩展到
钯催化的交叉偶联反应--药物的核心催化领域
化学反应。我们发现,~(13)C Kie的震级对~(13)C的微小变化高度敏感
RDS的TS处的碳-钯距离-使我们能够区分竞争对手
途径和探测金属中心的配体环境,所有这些都是在催化条件下进行的。最后,
我们已经开发了一种新的方法,利用对称的反应物在一个
与传统的KIE方法相比,时间和精力只是一小部分。
该Mira提案旨在进一步扩大我们的研究计划,以包括新的模式
现代有机合成前沿的催化作用:(A)钯催化的C-H键活化
和功能化,以及(B)镍金属光氧化还原催化。未来五年,我们的目标是
建立我们的实验和理论相结合的方法,作为获得原子学的最先进方法
对这些反应的机制基础的理解。我们选择了这两个领域来
扩大我们的研究计划有两个原因--(一)新的反应发现远远超过了
对这些反应的机理理解,以及(B)我们在钯催化的交叉反应中的发现。
耦合化学有力地表明,我们的方法非常适合于解决关键的机理
这些当代催化领域的问题。
我们研究计划的总体愿景是开发能够快速评估
催化反应的机理。我们寻求改变严格机械论的范式
理解是在新的反应发现之后进行的。我们设想高分辨率的机械论洞察力
我们的研究将激励人们发现新的、更强大的催化方法
将使有机合成成为可能。
项目成果
期刊论文数量(0)
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会议论文数量(0)
专利数量(0)
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Mathew J Vetticatt的其他文献
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{{ truncateString('Mathew J Vetticatt', 18)}}的其他基金
Novel Concepts and Mechanistic Probes in Catalysis
催化中的新概念和机理探索
- 批准号:
10059256 - 财政年份:2017
- 资助金额:
$ 39.05万 - 项目类别:
Novel Concepts and Mechanistic Probes in Catalysis
催化中的新概念和机理探索
- 批准号:
9929896 - 财政年份:2017
- 资助金额:
$ 39.05万 - 项目类别:
Novel Concepts and Mechanistic Probes in Catalysis
催化中的新概念和机理探索
- 批准号:
10304174 - 财政年份:2017
- 资助金额:
$ 39.05万 - 项目类别:
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