Enantiomeric Scaffolds for Organic Synthesis

描述（由申请人提供）：本文描述了容易制备的高对映体纯度的不饱和氧和氮杂环（η-3-吡喃基、η-3-吡啶基等）的钼π-络合物的设计和开发，其可以被充分官能化，然后以区域和立体控制的方式脱金属。从一个共同的手性支架，脱金属与功能化一致将研究三个核心协议：顺序功能化允许连接多个取代基，[5+2]和[5+3]环加成提供访问的氧杂和氮杂桥双环，和[4+2]环加成与烯基取代的eta-3-吡喃基和eta-3-吡啶基提供一个新的进入环稠合杂环。原则上，这些π-配合物作为高对映体纯度的手性支架用于取代的氧和氮杂环的快速组装 已知或潜在的药用价值。 除了基于溶液的方案的明显开发之外，金属络合物“支架” 方法应特别适合于使用平行的结构-活性-关系研究 合成技术这种“对映体纯支架”策略，如果发展到最大限度， 潜在的，可以举行很大的希望，快速SAR研究取代氧和氮 高对映纯度杂环体系。

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.