Catalytic Processes for Stereoselective Radical Cyclization Reactions
立体选择性自由基环化反应的催化过程
基本信息
- 批准号:10475223
- 负责人:
- 金额:$ 34.43万
- 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:2015-09-01 至 2023-08-31
- 项目状态:已结题
- 来源:
- 关键词:AddressAlkenesAzidesAziridinesBenignBiologicalCatalysisChemistryCobaltComplexCyclizationDevelopmentDissociationDrug IndustryEnvironmentExhibitsGenerationsGrantHeterocyclic CompoundsHydrogenIsomerismLeadLigandsMetalsMethodsModernizationMolecularMolecular StructureNatural ProductsNatureOrganic SynthesisPatternPeriodicityPharmaceutical PreparationsPharmacologic SubstancePlayPorphyrinsProcessReactionResearchSolventsSourceStructureSystemTestingToxic effectbasecatalystcost effectivecovalent bondcycloadditioncyclopropanedesigndiazo compounddrug candidatedrug developmentdrug discoveryenantiomerfunctional groupimprovednovel strategiesreaction ratesmall moleculestereochemistrytool
项目摘要
Cyclic structures, including both carbocycles and heterocycles, are common motifs of natural
products and synthetic compounds with important biomedical activities. Among different approaches
for preparing cyclic molecules, radical cyclization represents one of the most powerful approaches for
construction of ring structures. Among a number of inherent synthetic advantages, radical reactions
typically proceed at fast reaction rates under mild and neutral conditions in a broad spectrum of
solvents and exhibit significantly high functional group tolerance. Furthermore, radical processes have
the capability to perform in a cascade fashion, allowing for the rapid construction of complex molecular
structures with generation of multiple stereogenic centers. To further enhance the synthetic applications
of radical cyclization, new approaches will be needed for achieving high control of their reactivity as well
as stereoselectivity, especially enantioselectivity, challenging issues that are intrinsically associated
with the “free” nature of radical chemistry.
Guided by the concept of metalloradical catalysis (MRC), this proposed research explores a
fundamentally new approach for controlling stereoselectivity of both C- and N-centered radical
reactions. Cobalt(II) porphyrins [Co(Por)], as stable 15e metalloradicals, can enable the activation of
diazo compounds and organic azides to cleanly generate C- and N-centered radicals, respectively, with
N2 as the only byproduct in a controlled and catalytic manner. The initially-formed C- and N-centered
radicals, which are termed as a-Co(III)-alkyl radicals and a-Co(III)-aminyl radicals, respectively, remain
covalently bonded with [Co(Por)]. They can undergo common radical reactions, such as radical addition
to alkenes and hydrogen-atom abstraction, but with effective control of reactivity and stereoselectivity
by the porphyrin ligand environment. In addition to the radical nature of [Co(Por)], the low dissociation
energy of Co–C and Co–N bonds plays a key role for the successful turnover of the Co(II)-based
catalytic processes, resulting in effective radical cyclization reactions. Through the support of D2-
symmetric chiral porphyrin ligands with tunable electronic, steric, and chiral environments, Co(II)-based
metalloradical catalysis (Co(II)-MRC) will be applied for the development of various radical cyclization
processes for stereoselective construction of both carbocylic and N-heterocyclic compounds with
different ring sizes and varied degrees of molecular complexity.
We hope these studies will ultimately lead to the development of cost-effective and environmentally
benign radical cyclization processes that can be successfully applied for the stereoselective synthesis
of biologically important natural products and pharmaceutically interesting small molecules.
环结构,包括碳环和杂环,是自然界常见的基序
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(1)
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X. Peter ZHANG其他文献
X. Peter ZHANG的其他文献
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{{ truncateString('X. Peter ZHANG', 18)}}的其他基金
Stereoselective Radical Processes for C-H Alkylation and Amination
C-H 烷基化和胺化的立体选择性自由基过程
- 批准号:
10357917 - 财政年份:2020
- 资助金额:
$ 34.43万 - 项目类别:
Stereoselective Radical Processes for C-H Alkylation and Amination
C-H 烷基化和胺化的立体选择性自由基过程
- 批准号:
10557084 - 财政年份:2020
- 资助金额:
$ 34.43万 - 项目类别:
Stereoselective Radical Processes for C-H Alkylation and Amination
C-H 烷基化和胺化的立体选择性自由基过程
- 批准号:
10796195 - 财政年份:2020
- 资助金额:
$ 34.43万 - 项目类别:
Catalytic Processes for Stereoselective Radical Cyclization Reactions
立体选择性自由基环化反应的催化过程
- 批准号:
9543478 - 财政年份:2015
- 资助金额:
$ 34.43万 - 项目类别:
Catalytic Processes for Stereoselective Radical Cyclization Reactions
立体选择性自由基环化反应的催化过程
- 批准号:
10587778 - 财政年份:2015
- 资助金额:
$ 34.43万 - 项目类别:
Catalytic Processes for Stereoselective Radical Cyclization Reactions
立体选择性自由基环化反应的催化过程
- 批准号:
10018889 - 财政年份:2015
- 资助金额:
$ 34.43万 - 项目类别:
Catalytic Processes for Stereoselective Radical Cyclization Reactions
立体选择性自由基环化反应的催化过程
- 批准号:
10248461 - 财政年份:2015
- 资助金额:
$ 34.43万 - 项目类别:
Catalytic Processes for Stereoselective Radical Cyclization Reactions
立体选择性自由基环化反应的催化过程
- 批准号:
8887619 - 财政年份:2015
- 资助金额:
$ 34.43万 - 项目类别:
Catalytic Processes for Stereoselective Radical Cyclization Reactions
立体选择性自由基环化反应的催化过程
- 批准号:
9127979 - 财政年份:2015
- 资助金额:
$ 34.43万 - 项目类别:
New Catalytic Systems for Stereoselective C-H Amination
用于立体选择性 C-H 胺化的新型催化系统
- 批准号:
9188930 - 财政年份:2012
- 资助金额:
$ 34.43万 - 项目类别:
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