Radical redox catalysis by Ti complexes
Ti配合物的自由基氧化还原催化
基本信息
- 批准号:10798749
- 负责人:
- 金额:$ 15.65万
- 依托单位:
- 依托单位国家:美国
- 项目类别:
- 财政年份:2020
- 资助国家:美国
- 起止时间:2020-04-01 至 2024-06-30
- 项目状态:已结题
- 来源:
- 关键词:AddressAlcoholsAmidesCatalysisChemistryComplementComplexDevelopmentElectronsEpoxy CompoundsEventFree RadicalsGrantHydrogen BondingIsomerismLeadMediatingMedicineMethodologyNatureOrganic SynthesisOutcomeOxidation-ReductionParentsPreparationProcessReactionReagentResearchSiteSpeedStructureSystemTechniquesTechnologycatalystcycloadditioninnovationinsightinventionnovelnovel strategiesoxidationsuccesstool
项目摘要
Project Summary
This proposal focuses on uncovering new radical-based methodologies that facilitate the synthesis of
bioactive compounds. Organic radicals are highly reactive species with unique chemoselectivities that
complement canonical two-electron chemistry. Recently, the emergence of new reaction strategies that
leverage single-electron redox events and harness radical intermediates for the selective
functionalization of organic molecules has provided chemists with useful tools for solving contemporary
synthetic problems. However, the highly reactive nature of many organic radicals has made it difficult to
impart catalyst-control over the regio- and stereoselectivity of these fleeting intermediates, especially
when complex reaction systems are concerned. In particular, catalytic stereoselective reactions
involving free radical intermediates remain limited, and the discovery of such processes is highly
desirable. To provide new radical-based platforms for reaction discovery and synthetic innovation, we
developed catalytic strategies that leverage the unique redox features of low-valent Ti complexes to
achieve redox-neutral and net-reductive transformations, and through catalyst innovation, we
demonstrated that free-radical-mediated reactions can be made highly enantioselective. These
promising results prompted us to continue to invent novel catalytic and reaction strategies that can
effectively harness radical intermediates and provide powerful tools for solving a wide range of
longstanding synthetic problems. In the parent proposal, we aim to build upon our previous success but
move our research into new grounds. In each of the projects targeted herein, we aim to advance a new
approach that employ radical-based catalysts or reagents to address a prominent challenge in organic
synthesis. The transformations targeted in this grant are either currently unknown or display salient
limitations in reaction scope or selectivity. Among the specific reactions that we aim to develop in the
context of this grant are: enantioselective cycloadditions, enantioselective epoxide isomerizations,
oxidative desymmetrization of alcohols, enantioselective ⍺-oxidation of amides, and site-selective
functionalization of aliphatic C–H bonds. In addition, in-depth studies using canonical physical organic
and electroanalytical techniques will provide insights into the reaction mechanisms. The development
and mechanistic understanding of these proposed transformations will represent significant advances
for the field of organic synthesis.
项目摘要
本提案的重点是发现新的基于激进的方法,
生物活性化合物有机自由基是具有独特化学选择性的高活性物质,
补充正则双电子化学。最近,出现了新的反应策略,
利用单电子氧化还原事件和利用自由基中间体进行选择性
有机分子的功能化为化学家提供了解决当代问题的有用工具,
合成问题。然而,许多有机自由基的高反应性性质使得很难将其转化为有机自由基。
赋予催化剂对这些短暂中间体的区域和立体选择性的控制,特别是
当涉及到复杂的反应体系时。特别是催化立体选择性反应
涉及自由基中间体仍然有限,并且这些过程的发现是非常重要的。
令人向往为了为反应发现和合成创新提供新的基于自由基的平台,我们
开发了利用低价钛络合物独特的氧化还原特征的催化策略,
实现氧化还原中性和净还原转化,并通过催化剂创新,
证明了自由基介导的反应可以是高度对映选择性的。这些
有希望的结果促使我们继续发明新的催化和反应策略,
有效地利用自由基中间体,并提供强大的工具来解决广泛的
长期存在的合成问题。在母公司提案中,我们的目标是在以前成功的基础上再接再厉,
把我们的研究转移到新的领域在这里针对的每个项目中,我们的目标是推进一个新的
采用基于自由基的催化剂或试剂来解决有机化学中的突出挑战的方法
合成.本授权书中的目标转换要么是目前未知的,要么是突出的
反应范围或选择性的限制。在我们旨在发展的具体反应中,
该授权的内容是:对映选择性环加成,对映选择性环氧化物异构化,
醇的氧化去对称化,酰胺的对映选择性顺式氧化,和
脂肪族C-H键的官能化。此外,深入研究使用典型的物理有机
而电分析技术将提供对反应机理的深入了解。发展
对这些拟议的转变的机械理解将代表重大进展
在有机合成领域。
项目成果
期刊论文数量(10)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Titanium and Cobalt Bimetallic Radical Redox Relay for the Isomerization of N-Bz Aziridines to Allylic Amides.
- DOI:10.1055/s-0037-1610779
- 发表时间:2021
- 期刊:
- 影响因子:0
- 作者:Wood DP;Guan W;Lin S
- 通讯作者:Lin S
Enantioselective radical cascade cyclization via Ti-catalyzed redox relay.
- DOI:10.1016/j.tetlet.2023.154617
- 发表时间:2023-07
- 期刊:
- 影响因子:1.8
- 作者:Peng Yu;Wen Zhang;Song Lin
- 通讯作者:Peng Yu;Wen Zhang;Song Lin
Titanium Radical Redox Catalysis: Recent Innovations in Catalysts, Reactions, and Modes of Activation.
- DOI:10.1016/j.chempr.2022.06.005
- 发表时间:2022-07-14
- 期刊:
- 影响因子:23.5
- 作者:Wu, Xiangyu;Chang, Yejin;Lin, Song
- 通讯作者:Lin, Song
Deuterodehalogenation Under Net Reductive or Redox-Neutral Conditions Enabled by Paired Electrolysis.
通过配对电解实现净还原或氧化还原中性条件下的氘代脱卤。
- DOI:10.1002/anie.202218858
- 发表时间:2023
- 期刊:
- 影响因子:0
- 作者:Wood,Devin;Lin,Song
- 通讯作者:Lin,Song
An Electroreductive Approach to Radical Silylation via the Activation of Strong Si-Cl Bond.
- DOI:10.1021/jacs.0c10899
- 发表时间:2020-12-23
- 期刊:
- 影响因子:15
- 作者:Lu L;Siu JC;Lai Y;Lin S
- 通讯作者:Lin S
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{{ truncateString('Song Lin', 18)}}的其他基金
An electrocatalytic approach to discovering new synthetic transformations
发现新合成转化的电催化方法
- 批准号:
10406065 - 财政年份:2018
- 资助金额:
$ 15.65万 - 项目类别:
An electrocatalytic approach to discovering new synthetic transformations
发现新合成转化的电催化方法
- 批准号:
10001051 - 财政年份:2018
- 资助金额:
$ 15.65万 - 项目类别:
An electrocatalytic approach to discovering new synthetic transformations
发现新合成转化的电催化方法
- 批准号:
10463625 - 财政年份:2018
- 资助金额:
$ 15.65万 - 项目类别:
An electrocatalytic approach to discovering new synthetic transformations
发现新合成转化的电催化方法
- 批准号:
10677350 - 财政年份:2018
- 资助金额:
$ 15.65万 - 项目类别:
Electrochemistry as an enabling tool for reaction discovery
电化学作为反应发现的有利工具
- 批准号:
10659868 - 财政年份:2018
- 资助金额:
$ 15.65万 - 项目类别:
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