Enantiomeric Scaffolds for Organic Synthesis

描述（由申请人提供）：本文描述的是设计和开发易于制备的高对映纯度的不饱和氧和氮杂环（-3-吡喃基，-3-吡啶基等）钼pi配合物，这些配合物可以通过区域和立体控制的方式进行丰富的官能化和脱金属。从一个常见的手性支架，与功能化相一致的脱金属将通过三个核心方案进行研究：允许连接多个取代基的顺序功能化，[5+2]和[5+3]环加成提供了氧和氮桥的双环，以及[4+2]环加成与烯基取代的-3-吡喃和-3-吡啶基为环融合杂环提供了新的入口。原则上，这些pi-配合物作为高对映纯度的手性支架，用于取代氧和氮杂环的快速组装

DESCRIPTION (provided by applicant): Described herein are the design and development of easily prepared molybdenum pi-complexes of unsaturated oxygen and nitrogen heterocycles (eta-3-pyranyl, eta-3-pyridinyl, and others) of high enantiopurity, which can be richly functionalized then demetalated in a regio- and stereocontrolled fashion. From a common chiral scaffold, demetalation coincident with functionalization will be studied by three core protocols: sequential functionalization allowing attachment of multiple substituents, [5+2] and [5+3] cycloaddition providing access to oxa- and aza-bridged bicyclics, and [4+2] cycloadditions with alkenyl substituted eta-3-pyranyls and eta-3-pyridinyls giving a novel entry to ring-fused heterocycles. In principle, these pi-complexes function as chiral scaffolds of high enantiopurity for the rapid assembly of substituted oxygen and nitrogen heterocyclic systems of known or potential medicinal value. In addition to the obvious exploitation of solution-based protocols, the metal complex "scaffold" approach should be particularly amenable to structure-activity-relationship studies using parallel synthesis technologies. This "enantiomerically-pure scaffold" strategy, if developed to its fullest potential, could hold great promise for rapid SAR studies of substituted oxygen- and nitrogen heterocyclic systems of high enantiopurity.