Regiocontrolled Asymmetric alpha-Alkylation of Ketones via Activated Hydrazones

通过活化腙对酮进行区域控制的不对称 α-烷基化

• 批准号: 1305821
• 负责人: Don Coltart
• 金额: $ 10.49万
• 依托单位: University of Houston
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2012
• 资助国家: 美国
• 起止时间: 2012-10-01 至 2014-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1305821&HistoricalAwards=false
• 关键词: Regiocontrolled; Asymmetric; alpha; Alkylation; Ketones

In this project funded by the Chemical Synthesis program of the Chemistry Division, Professor Don M. Coltart of the Department of Chemistry at Duke University will explore the development of new methods for the regiocontrolled asymmetric alpha-alkylation of ketones. The central hypothesis of the planned research is that activated hydrazones - those having at least one electron withdrawing group on the distal nitrogen - and oximes will provide the basis for a variety of new approaches to the asymmetric alpha-alkylation of ketones. From this work, fundamentally new regiochemical substitution patterns that cannot be generated using existing technology will be accessible in an asymmetric manner. Moreover, it will be possible to conduct asymmetric alpha-alkylation in an umpolung sense, thus enabling the incorporation of functionality that cannot be introduced using enolate-based methods.This work could lead to facile methods for the asymmetric alpha-alkylation of ketones. The ability to easily and effectively prepare single enantiomer forms of alpha-alkylated ketones will contribute greatly to our ability to synthesize optically pure natural products, drugs and related compounds, thus impacting science and society in important ways. In addition, this project will provide excellent training of undergraduate and graduate students, including those from groups historically underrepresented in the sciences.

在化学部化学合成计划资助的该项目中，杜克大学化学系的Don M. Coltart教授将探索开发新方法，用于酮的不对称α-烷基化。 计划研究的中心假设是，活化的音证龙 - 远端氮的至少一个电子撤回组的音套 - Oximes将为各种新方法提供基础，以使酮的非对称α-烷基化。 从这项工作中，从根本上可以以不对称的方式访问无法使用现有技术产生的新的替代模式。此外，可以从umpolung的意义上进行不对称的α-烷基化，从而实现无法使用基于烯醇的方法引入的功能。这项工作可能会导致酮非对称α-烷基化的轻松方法。 轻松有效地制备单一对映异构体形式的α-烷基化酮的能力将极大地促进我们合成光学纯天然产品，药物和相关化合物的能力，从而以重要方式影响科学和社会。 此外，该项目将为本科生和研究生提供出色的培训，包括从历史上占科学人数不足的团体的培训。