Photoredox Catalysis in Organic Chemistry
有机化学中的光氧化还原催化
基本信息
- 批准号:9277495
- 负责人:
- 金额:$ 30.42万
- 依托单位:
- 依托单位国家:美国
- 项目类别:
- 财政年份:2010
- 资助国家:美国
- 起止时间:2010-04-01 至 2018-05-31
- 项目状态:已结题
- 来源:
- 关键词:3-hydroxybutanalAddressAldehydesAlkenesAlkylationAminationAminesAmino AcidsArchitectureAreaCarbonCatalysisComplexCouplingDecarboxylationDevelopmentDiaminesDisclosureElectronsFormaldehydeFundingGenerationsGrantHealthHomoHumanHydrogen BondingIminesIn SituIndustrializationIridiumKetonesLightMediatingMethaneMethodsOrganic ChemistryOrganic SynthesisOxidantsPharmacologic SubstanceProductionProtocols documentationReactionReducing AgentsReportingResearchResearch ProposalsRouteRutheniumSeminalSeriesSocietiesSulfhydryl CompoundsVariantVisible Radiationadductbasecatalystchemical reactionnovelprogramspublic health relevancescaffoldunnatural amino acids
项目摘要
DESCRIPTION (provided by applicant): Over the past five years, visible light-mediated photoredox catalysis has emerged as a versatile new activation platform in organic synthesis. Ruthenium or iridium-based polypyridyl photoredox catalysts absorb light in the visible range to generate stable, long-lived excited states that may act as either single-electron oxidants or reductants. Due to their unique reactivity profile, photoredox catalysts have the capacity to enable challenging bond constructions that are not accessible under standard approaches. In a seminal 2008 disclosure, our lab described the asymmetric α-alkylation of aldehydes via the synergistic merger of photoredox catalysis and chiral amine organocatalysis; this powerful dual-catalysis strategy features the simultaneous generation of catalytic quantities of both reactive intermediates. Subsequent reports, from our group and others, have further established the remarkable complexity-building capabilities of photoredox catalysis, particularly when merged with organocatalysis. In this research proposal, we outline new directions for our photoredox-based research program. Each of the four aims proposed herein envisions a novel reactivity platform featuring a transient, photoredox-generated active species that may be productively harnessed for the synthesis of a menu of high-value functional motifs. In Aim 1, we propose to develop direct, one-carbon expanded variants of the Mannich, Michael, and aldol reactions via a novel 5π-electron intermediate species that is transiently generated from ketone or aldehyde precursors through synergistic organocatalysis and photoredox catalysis. Aim 2 leverages an α-amino radical species - generated in situ via photoredox catalysis - en route to valuable amine-containing scaffolds, including vicinal diamines and allylic amines. Aim 3 envisions the direct arylation of labile allylic and benzylic C-H bonds through synergistic thiol-based organocatalysis and photoredox catalysis, as a means by which to gain rapid access to diaryl methanes and vinyl-aryl methanes. Finally, in Aim 4, we propose to accomplish the photoredox-catalyzed decarboxylative functionalization of
α-amino acids en route to valuable benzylic amine and alkyl amine motifs. In a key expansion of this project, we will explore opportunities for the development of an asymmetric variant for the synthesis of γ-amino aldehydes via merged photoredox and chiral amine-based organocatalysis.
描述(由申请人提供):在过去的五年中,可见光介导的光氧化还原催化已成为有机合成中一种多功能的新型活化平台,基于钌或铱的聚吡啶光氧化还原催化剂吸收可见光范围内的光以产生稳定的长光催化反应。 -可充当单电子氧化剂或还原剂的激发态由于其独特的反应性特征,光氧化还原催化剂能够实现具有挑战性的键结构。在 2008 年的一项开创性披露中,我们的实验室描述了通过光氧化还原催化和手性胺有机催化的协同合并可以实现醛的不对称 α-烷基化;这种强大的双重催化策略的特点是同时产生催化量的两种反应中间体随后的报告,来自我们的团队和其他人进一步确立了光氧化还原催化的显着的复杂性构建能力,特别是在这项研究中与有机催化合并时。在提案中,我们概述了基于光氧化还原的研究计划的新方向,其中提出的四个目标均设想了一个新颖的反应平台,该平台具有瞬态的光氧化还原生成的活性物质,可有效地用于合成一系列高价值的物质。在目标 1 中,我们建议通过一种新型 5π-电子中间体来开发曼尼希、迈克尔和羟醛反应的直接单碳扩展变体,该中间体是通过酮或醛前体瞬时产生的。协同有机催化和光氧化还原催化作用通过光氧化还原催化原位产生α-氨基自由基,形成有价值的含胺支架,包括邻位二胺和烯丙胺,目标3设想了不稳定烯丙基和苄基的直接芳基化。通过协同硫醇基有机催化和光氧化还原催化形成 C-H 键,如最后,在目标 4 中,我们建议实现二芳基甲烷和乙烯基芳基甲烷的光氧化还原催化脱羧功能化。
α-氨基酸正在转化为有价值的苄基胺和烷基胺基序 在该项目的关键扩展中,我们将探索通过合并光氧化还原和手性胺合成 γ-氨基醛的不对称变体的开发机会。有机催化。
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)
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David W MacMillan其他文献
David W MacMillan的其他文献
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{{ truncateString('David W MacMillan', 18)}}的其他基金
Photoredox Catalysis Applications in Organometallics and Chemical Biology
光氧化还原催化在有机金属学和化学生物学中的应用
- 批准号:
10077569 - 财政年份:2020
- 资助金额:
$ 30.42万 - 项目类别:
Photoredox Catalysis Applications in Organometallics and Chemical Biology
光氧化还原催化在有机金属学和化学生物学中的应用
- 批准号:
10544541 - 财政年份:2020
- 资助金额:
$ 30.42万 - 项目类别:
Photoredox Catalysis Applications in Organometallics and Chemical Biology
光氧化还原催化在有机金属学和化学生物学中的应用
- 批准号:
10326379 - 财政年份:2020
- 资助金额:
$ 30.42万 - 项目类别:
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