Regiocontrolled Asymmetric alpha-Alkylation of Ketones via Activated Hydrazones

在这个由化学系化学合成项目资助的项目中，Don M.杜克大学化学系的Coltart将探索开发酮的区域控制不对称α-烷基化的新方法。 计划中的研究的中心假设是，活化的腙-那些在远端氮上至少有一个吸电子基团-和肟将为酮的不对称α-烷基化的各种新方法提供基础。 从这项工作中，根本上新的区域化学取代模式，不能使用现有的技术产生将以不对称的方式访问。此外，它将有可能进行不对称的α-烷基化在一个umpolung意义上，从而使功能，不能使用烯醇化物为基础的方法引入incorporations.This工作可能会导致简便的方法为酮的不对称α-烷基化。 容易且有效地制备α-烷基化酮的单一对映体形式的能力将极大地有助于我们合成光学纯天然产物、药物和相关化合物的能力，从而以重要的方式影响科学和社会。 此外，该项目还将为本科生和研究生提供出色的培训，包括那些来自历史上在科学领域代表性不足的群体的学生。

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.