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.

在这个由化学系化学结构、动力学机制B计划资助的项目中，科尔比学院化学系的Dasan Thamattoor教授正在开发含有三键的小环化合物的新方法。由于三键更倾向于线性几何形状，因此将该特征结合在小环内可能导致相当大的应变。研究这种应变分子可以教我们关于结构，键合，能量学和化学反应性。它可以导致设计新的反应，用于制备药物和高能材料。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经验，并让他们成为科学企业的合作伙伴。此外，还将采取若干举措，促进在当地学校（K-12）提供科学、技术、工程和数学（STEM）方面的高质量教育。这包括为高中生提供暑期研究机会，并与小学，初中和初中的教育工作者合作，以加强STEM课程。该项目包含一套目标，适合本科生驱动的研究计划，以产生应变环炔从新的光化学和热源。这些来源是基于环丙烷化菲和茚满系统，并进行研究，以产生已知的和新的碳环，杂环和多环炔。 基质分离和时间分辨激光闪光光解将被用来研究环亚烷基卡宾中间体的动力学。闪速真空热解将研究作为一种补充方法的光化学路线产生这些应变环炔。应变环炔的化学，相对于它们形成和消耗的途径，也将通过现代计算方法进行研究。

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.