Green Chemistry for Catalytic Carbonyl Propargylation

催化羰基炔丙基化的绿色化学

• 批准号: 1008551
• 负责人: Michael Krische
• 金额: $ 45万
• 依托单位: University of Texas at Austin
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2010
• 资助国家: 美国
• 起止时间: 2010-09-15 至 2014-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1008551&HistoricalAwards=false
• 关键词: Green; Chemistry; Catalytic; Carbonyl; Propargylation

This project focuses on the development of metal-catalysts that promote direct byproduct-free C-C coupling of alcohols and pi-unsaturated compounds. In the proposed funding period, this novel pattern of reactivity will be applied to enyne-mediated propargylation of carbonyl compounds from the alcohol oxidation level. A feature of these transformations is the ability to achieve carbonyl addition directly from the alcohol oxidation state by exploiting alcohols and conjugated enynes as redox-pairs. Here, alcohol dehydrogenation drives reductive generation of allenylmetal species and aldehyde electrophiles, which combine to furnish homo-propargyl alcohols. Unlike classical approaches to carbonyl propargylation, which require carbonyl electrophiles in combination with pre-metallated nucleophiles (e.g. organo-tin or organo-magnesium reagents), the C-C coupling processes employ pi-unsaturated compounds as surrogates to pre-metallated nucleophiles, thus avoiding generation of stoichiometric metallic waste. Further, through the direct C-C coupling of alcohols, one circumvents discrete redox manipulations otherwise required for pre-generation of aldehyde electrophiles. With this award, the Chemical Synthesis Program is supporting the research of Professor Michael J. Krische of the Department of Chemistry and Biochemistry at the University of Texas at Austin. Professor Krische, who leads the Center for Green Chemistry and Catalysis, is engaged in the development of catalytic C-C bond forming processes that enable sustainable, byproduct-free manufacture of chemical products from abundant, renewable resources. Successful development of the methodology will have an impact on any area of activity in which the synthesis of organic molecules is needed, such as the pharmaceutical, chemical, agricultural industry, and the biological and chemical research activities. In addition, this project will provide excellent training of students, from pre-undergraduate to post-doctoral, including those from groups historically underrepresented in the sciences.

该项目重点开发金属催化剂，促进醇和π不饱和化合物的直接无副产物C-C偶联。 在拟议的资助期内，这种新颖的反应模式将应用于烯炔介导的醇氧化水平的羰基化合物的炔丙基化。 这些转化的一个特点是能够通过利用醇和共轭烯炔作为氧化还原对，直接从醇氧化态实现羰基加成。 在这里，醇脱氢驱动烯基金属物质和醛亲电子试剂的还原生成，它们结合形成均炔丙醇。 传统的羰基炔丙基化方法需要羰基亲电子试剂与预金属化亲核试剂（例如有机锡或有机镁试剂）结合，而C-C偶联过程则采用π不饱和化合物作为预金属化亲核试剂的替代物，从而避免产生化学计量的金属废物。 此外，通过醇的直接 C-C 偶联，可以避免预生成醛亲电子试剂所需的离散氧化还原操作。化学合成项目通过该奖项支持德克萨斯大学奥斯汀分校化学与生物化学系 Michael J. Krische 教授的研究。 Krische 教授领导绿色化学和催化中心，致力于开发催化 C-C 键形成工艺，利用丰富的可再生资源实现可持续、无副产品的化学产品制造。 该方法的成功开发将对需要合成有机分子的任何活动领域产生影响，例如制药、化学、农业以及生物和化学研究活动。 此外，该项目将为从本科预科到博士后的学生提供出色的培训，包括来自历史上在科学领域代表性不足的群体的学生。