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.

在由化学结构，动态和机制B计划资助的该项目中，Colby College化学系的Dasan Thamattoor教授正在开发新的方法，用于包含三重债券的小环化合物。当三键更喜欢线性几何形状时，将此特征结合在一个小环内会导致相当大的应变。研究这种紧张的分子可以教给我们有关结构，键合，能量和化学反应性的知识。它可以为制剂设计新反应和能量材料的制备。该项目整合了合成，机械和计算有机化学的要素，旨在为大学生提供有益健康的研究经验，并在科学企业中作为合作伙伴与他们互动。此外，还将采用几项促进当地学校（K-12）中科学，技术，工程和数学（STEM）提供高质量教育的举措。这包括为高中生提供夏季的研究机会，并与小学，初中和初中的教育者合作，以增强STEM产品。该项目包含一组目标，适合本科驱动的研究计划，可从新的光化学和热源来源产生紧张的环虫。这些来源基于环丙烷的光毒和Indan系统，应研究以生成已知和新的碳环，杂环和多环芳烃的生成。 基质分离和时间分辨激光光解会用于研究环烷基烯烃中间体的动力学。闪光真空热解将作为用于产生这些紧张的环虫的光化学途径的互补方法。关于形成和消耗的途径，紧张的环虫的化学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.

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.

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.