New directions in asymmetric organocatalysis

拟议的研究计划旨在通过开发新型催化剂及其在新反应中的应用，扩大有机催化的范围。利用有机分子进行不对称催化（有机催化）是近年来以对映选择性方式合成有机化合物的一种强有力的方法。尽管在这一领域取得了巨大的进步，但迄今为止开发的大多数方法都显示出试剂的范围很窄。此外，迄今为止报道的催化剂在其支架和催化性质上几乎没有变化。本研究的目的是开发新的有机催化剂类别和新的催化作用模式，以补充和扩展现有的方法。为了实现这些目标，将探索三个不同的领域：不对称相转移催化，多功能催化和Lewis碱催化Diels-Alder反应。在本计划的第一部分，将合成具有新型支架的相转移催化剂，以扩大这类催化剂的范围并提高其稳定性。在多功能催化领域，将介绍各种类型的激活基团，如取代胍。这些基团将显示出更高的反应活性，以及通过明智地选择取代基来调整活性的能力。最后，路易斯碱催化剂在Diels-Alder反应中的应用将极大地扩大这一重要反应的可用反应伙伴的范围。特别是，它将允许使用各种各样的功能化二烯，这些二烯与常用的路易斯酸催化剂不相容。本研究项目的基本主题是利用有机分子作为催化剂，进行有用化学构件的不对称合成。

The proposed research program aims at expanding the scope of organocatalysis as it stands today through the development of new classes of catalysts and their application to new reactions.  Asymmetric catalysis using organic molecules (organocatalysis) has recently emerged as a powerful approach for the synthesis of organic compounds in an enantioselective fashion. Despite the great advances accomplished in this area, most methods developed so far show a narrow scope of reagents. Also, the catalysts reported to date show very little variety in their scaffold and the nature of their catalysis. The purpose of this research is to develop new classes of organocatalysts and new catalytic modes of action that will complement and expand existing methodology. In order to achieve these goals, three different areas will be explored: asymmetric phase transfer catalysis, multifunctional catalysis, and Lewis base-catalyzed Diels-Alder reactions.   In the first part of the program, phase transfer catalysts possessing novel scaffolds will be synthesized in order to broaden the scope and to improve the stability of this type of catalysts. In the area of multifunctional catalysis, various types of activating groups, such as substituted guanidines, will be introduced. These groups will display increased reactivity as well as the ability to tune their activity through the judicious choice of their substituents. Finally, the application of Lewis base catalysts to the Diels-Alder reaction will dramatically expand the scope of available reactive partners for this very important reaction. In particular, it will allow the use of a wide variety of functionalized dienes that are incompatible with commonly used Lewis acid catalysts.   The underlying theme of this research program is the asymmetric synthesis of useful chemical building blocks using organic molecules as catalysts.