RUI: Strained Cycloalkynes

RUI：应变环炔

• 批准号: 1665278
• 负责人: Dasan Thamattoor
• 金额: $ 29.86万
• 依托单位: Colby College
• 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: 2017-07-01 至 2021-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1665278&HistoricalAwards=false
• 关键词: RUI; Strained; Cycloalkynes

In this project funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor Dasan Thamattoor of the Department of Chemistry at Colby College is developing new approaches to small-ring compounds containing a triple bond. As the triple bond prefers a linear geometry, incorporating this feature inside a small ring can lead to considerable strain. Investigating such strained molecules can teach us about structure, bonding, energetics, and chemical reactivity. It can lead to the design of new reactions for the preparations of pharmaceuticals and energetic materials. The project, which integrates elements of synthetic, mechanistic, and computational organic chemistry, is designed to provide undergraduates with a wholesome research experience, and engage them as partners in the scientific enterprise. In addition, several initiatives to promote the delivery of high quality education in Science, Technology, Engineering, and Mathematics (STEM) in the local schools (K-12) will be pursued. This includes providing summer research opportunities for high school students and partnering with educators in the elementary, middle, and junior high schools to enhance STEM offerings. The project contains a set of aims, appropriate for an undergraduate-driven research program, to generate strained cycloalkynes from new photochemical and thermal sources. These sources are based on cyclopropanated phenanthrene and indan systems and are to be studied for the generation of known and new carbocyclic, heterocyclic, and polycyclic alkynes. Matrix isolation and time-resolved laser flash photolysis will be used to study the kinetics of the cyclic alkylidenecarbene intermediates. Flash vacuum pyrolysis will be studied as a complementary approach to the photochemical route for generating these strained cycloalkynes. The chemistry of strained cycloalkynes, with respect to the pathways by which they are formed and consumed, will also be investigated by modern computational methods.

在这项由化学系化学结构、动态和机理B计划资助的项目中，科尔比学院化学系的Dasan Thamattoor教授正在开发包含三个键的小环化合物的新方法。由于三键更倾向于线性几何结构，将这一特征加入到一个小环中可能会导致相当大的张力。研究这种应变分子可以教给我们关于结构、成键、能量学和化学反应的知识。它可以为药物和含能材料的制备提供新的反应设计。该项目整合了合成、机械和计算有机化学的元素，旨在为本科生提供健康的研究体验，并让他们成为科学事业的合作伙伴。此外，还将采取若干举措，促进在当地学校(K-12)提供高质量的科学、技术、工程和数学教育。这包括为高中生提供暑期研究机会，并与小学、中学和初中的教育工作者合作，加强STEM课程。该项目包含一系列目标，适用于本科生主导的研究计划，目的是从新的光化学和热源中产生应变环炔。这些来源基于环丙基菲和吲哚体系，并将用于研究已知的和新的碳环、杂环和多环炔的生成。用基质分离和时间分辨激光闪光光解方法研究了环烷基卡宾中间体的动力学。闪速真空热解将作为产生这些应变环炔的光化学途径的补充方法而被研究。还将用现代计算方法研究应变环炔的化学，以及它们形成和消耗的途径。

项目成果

Ring Expansion of Alkylidenecarbenes Derived from Lactams, Lactones, and Thiolactones into Strained Heterocyclic Alkynes: A Theoretical Study

• DOI: 10.3390/molecules24030593
• 发表时间: 2019-02
• 期刊: Molecules
• 影响因子: 4.6
• 作者: Nguyen Nhat Thu Le;Josefine Just;Jonathan M. Pankauski;P. Rablen;D. Thamattoor

Photochemical generation and trapping of 3-oxacyclohexyne

• DOI: 10.1039/c7ob01697b
• 发表时间: 2017-10-21
• 期刊: ORGANIC & BIOMOLECULAR CHEMISTRY
• 影响因子: 3.2
• 作者: Fan, Rui;Wen, Yuewei;Thamattoor, Dasan M.
• 通讯作者: Thamattoor, Dasan M.

Direct Observation of an Alkylidenecarbene by Ultrafast Transient Absorption Spectroscopy

• DOI: 10.1021/acs.jpca.8b06118
• 发表时间: 2018-08-30
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY A
• 影响因子: 2.9
• 作者: Du, Lili;Lan, Xin;Thamattoor, Dasan M.
• 通讯作者: Thamattoor, Dasan M.

Stereochemistry of Dichlorocarbene Addition to Alkenes: A Collaborative, Discovery-Based Experiment for the Organic Chemistry Laboratory

二氯卡宾与烯烃加成的立体化学：有机化学实验室的基于发现的协作实验

• DOI: 10.1021/acs.jchemed.8b00758
• 发表时间: 2019
• 期刊: Journal of Chemical Education
• 影响因子: 3
• 作者: Thu Le, Nguyen Nhat;Klinkerch, Edmund J.;Thamattoor, Dasan M.
• 通讯作者: Thamattoor, Dasan M.

Double trap: A single product from the THF-initiated interception of a cyclopropylidene(oid) and its rearranged strained cyclic allene

双陷阱：由 THF 引发的亚环丙烷基及其重排应变环状丙二烯的截获的单一产物

• DOI: 10.1016/j.molstruc.2018.01.061
• 发表时间: 2018
• 期刊: Journal of Molecular Structure
• 影响因子: 3.8
• 作者: Esquivel-Amores, Ernesto;Rogers, Kirstie;Thamattoor, Luca R.;Thamattoor, Dasan M.
• 通讯作者: Thamattoor, Dasan M.