Catalytic Cycloaddition Reactions and Their Applications

催化环加成反应及其应用

• 批准号: 2054845
• 负责人: Michael Doyle
• 金额: $ 48.31万
• 依托单位: University of Texas at San Antonio
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-08-01 至 2024-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2054845&HistoricalAwards=false
• 关键词: Catalytic; Cycloaddition; Reactions; Their; Applications

With the support of the Chemical Catalysis (CAT) and Chemical Synthesis (SYN) Programs in the Division of Chemistry, Professor Michael Doyle of the University of Texas, San Antonio is working to develop new ways to construct molecules using vinyl diazo compounds, organic building blocks that have a carbon-carbon double bond next to an electron-poor carbon, formally known as a carbenoid center. Catalysts are being studied to tune and control the reactivity of vinyl diazo compounds with compatible reagents to access value-added products. These investigations are working toward establishing new ways to construct challenging bonds and heteroaromatic structures that are common components of valued added target molecules, particularly heterocyclic structures of value to biological and medicinal chemistry. Synergistically, these activities will provide opportunities for students of different levels to broaden their knowledge and experience in catalytic and synthetic chemistry. Undergraduate students are being integrated into the research program with strong mentoring that prepares them for careers in STEM (science, technology, engineering and mathematics) disciplines, and opportunities are being provided to postdoctoral research associates to prepare them for positions in the chemical sciences in both the private sector and in academia.New modular methods for the synthesis of heterocycles and functionalized carbocycles are in high demand due to the prevalence of these structures in pharmaceutical, agrochemical, and new material targets. Professor Michael Doyle and his research team are identifying catalysts that extrude molecular nitrogen from vinyl diazo-compounds to form highly energetic metallocarbene intermediates that condense with a variety of dipolar cycloaddition partners to form novel adduce with a high degree of regio- and stereo control. The stereodefined products of [3+1]-cycloaddition reactions of silyl-protected enoldiazo compounds will be studied for subsequent strain-induced ring-opening reactivity and used to explore cycloaddition reactions of donor-acceptor cycloalkenes. Acid-catalyzed conditions with triflimide are being developed to engage vinyl diazo [3+1] cycloaddition products in subsequent cycloaddition reactions that lead to intermediate structures capable of ring expansion to medium-sized products. Highly enantioselective catalytic cyclopropanation reactions of enoldiazo compounds are being tested to prepare donor-acceptor cyclopropanes that are capable of engaging in cycloaddition reactions with retention of enantioenrichement. These activities will take place at the University of Texas, San Antonio, and augment the inclusive training and research opportunities at this minority-serving institution.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学系化学催化（CAT）和化学合成（SYN）项目的支持下，德克萨斯大学圣安东尼奥分校的迈克尔·多伊尔（Michael Doyle）教授正致力于开发利用乙烯基重氮化合物构建分子的新方法。重氮化合物是一种有机构建块，其碳-碳双键紧挨着一个电子贫碳，正式称为类碳中心。人们正在研究催化剂，以调节和控制乙烯基重氮化合物与相容试剂的反应性，以获得增值产品。这些研究正致力于建立新的方法来构建具有挑战性的键和杂芳香结构，这些结构是有价值的目标分子的共同组成部分，特别是对生物和药物化学有价值的杂环结构。这些活动将为不同水平的学生提供机会，以扩大他们在催化和合成化学方面的知识和经验。本科生被整合到研究项目中，得到强有力的指导，为他们在STEM（科学、技术、工程和数学）学科的职业生涯做好准备，并为博士后研究助理提供机会，为他们在私营部门和学术界的化学科学职位做好准备。由于杂环和功能化碳环在制药、农化和新材料靶标中的广泛应用，对新的模块化合成方法有着很高的需求。Michael Doyle教授和他的研究小组正在寻找催化剂，从乙烯基重氮化合物中挤出分子氮，形成高能量的金属卡宾中间体，与各种偶极环加成伙伴凝聚，形成具有高度区域和立体控制的新型内合物。研究了受硅基保护的烯二偶氮化合物[3+1]-环加成反应的立体定义产物，用于随后的菌株诱导开环反应，并用于探索供体-受体环烯烃的环加成反应。目前正在开发三氟氰酸催化条件，以使乙烯基重氮[3+1]环加成产物在随后的环加成反应中产生能够扩环到中等大小产物的中间结构。对烯诺二偶氮化合物的高对映选择性催化环丙烷化反应进行了测试，以制备能够参与环加成反应并保留对映体富集的供体-受体环丙烷。这些活动将在德克萨斯大学圣安东尼奥分校举行，并在这所为少数族裔服务的机构中增加包容性培训和研究机会。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Diverse Reactions of Vinyl Diazo Compounds with Quinone Oxonium Ions, Quinone Imine Ketals, and Eschenmoser’s Salt

• DOI: 10.1021/acscatal.1c02674
• 发表时间: 2021-08
• 期刊: ACS Catalysis
• 影响因子: 12.9
• 作者: Haifeng Zheng;Kan Wang;Isa Faghihi;W. Griffith;Hadi D Arman;M. Doyle

Stereoretentive Catalytic [3+2]-Cycloaddition/Rearrangement/Decarboxylation Reactions of Indoles with Non-Racemic Donor–Acceptor Cyclopropanes

• DOI: 10.1021/acscatal.2c05930
• 发表时间: 2023-01
• 期刊: ACS Catalysis
• 影响因子: 12.9
• 作者: M. Bao;K. Lopez;Rajesh Gurung;Hadi D Arman;M. Doyle