Selective Oxidation of Primary C-H Bonds Using Late-Transition-Metal-Oxo Catalysts
使用后过渡金属氧合催化剂选择性氧化初级 C-H 键
基本信息
- 批准号:10387337
- 负责人:
- 金额:$ 6.68万
- 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:2022-03-01 至 2025-02-28
- 项目状态:未结题
- 来源:
- 关键词:AlcoholsArchitectureAreaAttentionCarbonChemicalsComplexCouplingDevelopmentDrug IndustryHealthHumanHydrogen BondingIn SituIndustryKineticsLigandsMedicineMetalsMethodologyMethodsNatural ProductsOrganic ChemistryOrganometallic CompoundsOxidantsOxygenPharmaceutical ChemistryPharmaceutical PreparationsPharmacologic SubstancePhysical condensationPreparationProductionReactionResearchRoleRouteSeriesSiteStructureStructure-Activity RelationshipSynthesis ChemistryTechnologyTransition Elementsanalogcarbenecatalystchemical propertychemical synthesiscomparativedrug discoveryelectronic structurefunctional grouphydroxyl groupimprovedinnovationinsightmethyl groupnext generationnitrenenoveloxeneoxidationpreventscaffoldsmall moleculetooltrend
项目摘要
Project Summary/Abstract
Advances in organic synthetic methodology can profoundly impact the development of new and useful
medicines. For example, cross-coupling reactions have become indispensable tools in medicinal chemistry,
provided entry to previously inaccessible chemical space, and enhanced drug discovery efforts. Recently,
methods for the selective functionalization of C–H bonds have gained attention from the pharmaceutical industry
due to their potential utility in the diversification of drug-like scaffolds. Toward this end, metal-catalyzed C–H
functionalization reactions that take advantage of polar functional groups to direct site-selective C–H activation
have been extensively explored. In comparison, methods that avoid the use of pre-installed directing groups, or
“undirected” C–H functionalization reactions, are underdeveloped. Specifically, the selective and undirected
metal-catalyzed activation of strong primary C(sp3)–H bonds in the presence of weaker C–H bonds represents
an ongoing challenge in the field. Notably, such technologies would provide chemists with useful synthetic tools
to install functionality at remote sites on bioactive molecules. Though methods for the undirected selective
catalytic functionalization of methyl groups to forge C–C, C–B, and C–Cl bonds have recently emerged, a general
catalytic oxidation (C–O bond formation) of unactivated primary C(sp3)–H bonds is unknown.
Metal-stabilized carbenes, nitrenes, and oxenes are useful reactive intermediates that can insert carbon or
heteroatom functionality into strong C(sp3)–H bonds with ligand-controlled selectivities. Although early- and mid-
first-row transition-metal-oxo complexes have been intensively studied, first-row late-transition-metal-oxo
species (LTM-oxo) are less explored despite their potential utility for C–H oxidation. Indeed, synthesizing LTM-
oxo complexes represents a major challenge toward harnessing these highly reactive species as useful oxidants.
The proposed research aims to develop a modular route toward a series of LTM-oxo complexes bearing a novel
sterically-bulky triptycene-substituted dipyrrin ligand scaffold. This ligand architecture is expected to enforce
kinetic stability of the complexes to facilitate isolation and characterization efforts. The ligand scaffold will also
promote high-spin electronic configurations, which should weaken the M–O bond and render the complexes
more reactive toward C(sp3)–H oxidation. Finally, the reactivity of transiently-formed and sterically encumbered
LTM-oxo complexes will be harnessed to enable the selective and undirected catalytic oxidation of sterically
unhindered methyl groups. This methodology will also be applied toward the selective late-stage functionalization
of medicinally-relevant scaffolds. These efforts will result in the first general method for the catalytic undirected
oxidation of primary C(sp3)–H bonds. Moreover, these studies will provide the first unambiguous characterization
of high-spin LTM-oxo complexes and validate their synthetic utility for catalytic C–H oxidation.
项目总结/文摘
项目成果
期刊论文数量(0)
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Timothy Bartlett Boit其他文献
Timothy Bartlett Boit的其他文献
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{{ truncateString('Timothy Bartlett Boit', 18)}}的其他基金
Selective Oxidation of Primary C-H Bonds Using Late-Transition-Metal-Oxo Catalysts
使用后过渡金属氧合催化剂选择性氧化初级 C-H 键
- 批准号:
10555189 - 财政年份:2022
- 资助金额:
$ 6.68万 - 项目类别:
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