权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Excited state intramolecular proton transfer-based photoassisted methodologies to access complex molecular architectures

基于激发态分子内质子转移的光辅助方法来获取复杂的分子结构

基本信息

批准号：
1665342
负责人：
Andrei Kutateladze
金额：
$ 37.14万
依托单位：
University of Denver
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2017
资助国家：
美国
起止时间：
2017-09-01 至 2020-08-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1665342&HistoricalAwards=false
关键词：
Excited state intramolecular proton transfer

项目摘要

In this project funded by the Chemical Synthesis Program, Professor Andrei Kutateladze of the Department of Chemistry and Biochemistry at University of Denver develops new methods for the synthesis of complex organic heterocycles. These are substances which contain nitrogen in a ring, a common feature of natural products and pharmaceuticals. New synthetic routes are primarily based on novel cycloaddition reactions initiated by ultraviolet light. Complex multi-ring heterocyclic molecular architectures are accessed and alkaloid mimics are synthesized. Fundamental new science includes the development of cascade photoreactions to form multiple chemical bonds in one experimentally simple step. In addition, this award supports research experiences for undergraduate and graduate students, especially those from historically underrepresented groups in science.This research expands the excited state intramolecular proton transfer (ESIPT) based synthetic photochemistry tool box with new photoassisted cascade methodology. New reactions provide access to complex polyheterocyclic compounds in a controlled atom- and step-economical fashion. The mechanism of these cascade processes, including quantum mechanical tunneling at the hydrogen transfer step, is elucidated to better modulate stereochemical and regiochemical outcomes. Such control is needed to develop the capability of systematically screening the chemical space in search of novel polyheterocyclic molecular architectures with the requisite scaffold diversity. To further grow scaffold complexity and diversity and to decorate the core scaffolds with additional functional groups and heterocyclic pendants, experimentally simple postphotochemical steps are deployed after the light-induced transformation. This experimental work is accompanied by the development of computational methods for fast and accurate predictions of NMR spectra, which is critical for success of this project, but also has broader implications for structure elucidation of complex synthetic and natural organic molecules. Additionally, this research provides hands-on laboratory training for graduate and undergraduate students, especially those from historically underrepresented groups in science.

在这个由化学合成计划资助的项目中，丹佛大学化学和生物化学系的Andrei Kutateladze教授开发了合成复杂有机杂环的新方法。这些物质在环中含有氮，这是天然产品和药物的共同特征。新的合成路线主要是基于紫外光引发的新型环加成反应。获得复杂的多环杂环分子结构并合成生物碱模拟物。基础新科学包括级联光反应的发展，在一个实验简单的步骤中形成多个化学键。此外，该奖项还支持本科生和研究生的研究经验，特别是那些来自科学领域历史上代表性不足的群体的研究经验。这项研究扩展了基于激发态分子内质子转移（ESIPT）的合成光化学工具箱，采用新的光辅助级联方法。新的反应以可控的原子和步骤经济的方式提供了获得复杂的多杂环化合物的途径。阐明这些级联过程的机制，包括氢转移步骤的量子力学隧道效应，以更好地调节立体化学和区域化学结果。需要这种控制来开发系统地筛选化学空间以寻找具有所需支架多样性的新型多杂环分子结构的能力。为了进一步增加支架的复杂性和多样性，并用额外的官能团和杂环侧基装饰核心支架，在光诱导转化后部署实验上简单的光化学后步骤。这项实验工作伴随着快速准确预测NMR光谱的计算方法的发展，这对该项目的成功至关重要，但也对复杂合成和天然有机分子的结构解析具有更广泛的意义。此外，这项研究还为研究生和本科生提供了动手实验室培训，特别是那些来自历史上代表性不足的科学群体的学生。

项目成果

期刊论文数量（14）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Structure Validation of Complex Natural Products: Time to Change the Paradigm. What did Synthesis of Alstofolinine A Prove?

DOI：
10.1021/acs.joc.9b00969
发表时间：
2019-06-21
期刊：
JOURNAL OF ORGANIC CHEMISTRY
影响因子：
3.6
作者：
Kutateladze, Andrei G.;Holt, Tina
通讯作者：
Holt, Tina

The Discreet Structural Diversity of Briarellins: DU8+ Guided Multiple Structure Revisions Yielded Two Unknown Structural Types

Briarellins 的谨慎结构多样性：DU8 引导的多重结构修改产生了两种未知的结构类型

DOI：
10.1021/acs.joc.0c00555
发表时间：
2020
期刊：
The Journal of Organic Chemistry
影响因子：
0
作者：
Holt, Tina A.;Reddy, D. Sai;Huple, Deepak B.;West, Lyndon M.;Rodríguez, Abimael D.;Crimmins, Michael T.;Kutateladze, Andrei G.
通讯作者：
Kutateladze, Andrei G.

Step-Economical Photoassisted Diversity-Oriented Synthesis: Sustaining Cascade Photoreactions in Oxalyl Anilides to Access Complex Polyheterocyclic Molecular Architectures

DOI：
10.1021/jacs.7b07598
发表时间：
2017-11-22
期刊：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
影响因子：
15
作者：
Kuznetsov, Dmitry M.;Kutateladze, Andrei G.
通讯作者：
Kutateladze, Andrei G.

Diastereoselective heterocyclization of geminal bromo-fluoro arylcyclopropanes by nitrosonium tetrafluoroborate: Access to 4-fluorinated isoxazolines and isoxazoles

四氟硼酸亚硝基对偕溴氟芳基环丙烷的非对映选择性杂环化：获得 4-氟化异恶唑啉和异恶唑

DOI：
10.1016/j.tet.2019.130666
发表时间：
2019
期刊：
Tetrahedron
影响因子：
2.1
作者：
Bondarenko, Oksana B.;Komarov, Arseniy I.;Karetnikov, George L.;Nikolaeva, Svetlana N.;Zyk, Nikolai V.;Holt, Tina;Kutateladze, Andrei G.
通讯作者：
Kutateladze, Andrei G.

Natural Products Containing the Oxetane and Related Moieties Present Additional Challenges for Structure Elucidation: A DU8+ Computational Case Study