Rhodium-Catalysed Ynamide Carbometallations for Stereoselective Synthesis

烯酰胺是含有与氮原子连接的碳-碳双键的化合物，所述氮原子本身与吸电子官能团键合。烯酰胺是近年来出现的一系列有用的化学反应的多用途合成中间体。然而，以完全受控的方式合成高度取代的酰胺通常具有高度挑战性，并且这种限制阻碍了对其化学的充分探索。拟议的研究旨在开发最近发现的一种反应，该反应能够控制高度取代的酰胺的合成。该反应在温和的条件下进行，并使用市售的铑配合物作为预催化剂，沿着有机锌化合物作为有机金属试剂。使用这种化学方法可以获得相当广泛的烯酰胺，初步研究表明，这些新化合物在各种反应中显示出有用的反应活性。然而，需要更多的工作来充分开发烯酰胺合成本身和烯酰胺产物的合成应用的范围。这些目标是本建议的核心。

Enamides are compounds that contain a carbon-carbon double bond attached to a nitrogen atom that is itself bonded to an electron-withdrawing functional group. Enamides have recently emerged as versatile synthetic intermediates for a range of useful chemical reactions. However, the synthesis of highly substituted enamides in a fully controlled fashion is often highly challenging, and this limitation hampers full exploration of their chemistry. The proposed research is aimed at the development of a recently discovered reaction that enables the controlled synthesis of highly substituted enamides. This reaction proceeds under mild conditions, and employs a commercially available rhodium complex as a precatalyst along with organozinc compounds as organometallic reagents. A reasonably wide range of enamides can be accessed using this chemistry, and preliminary investigations suggest that these new compounds display useful reactivities in a variety of reactions. However, much more work is required to fully develop the scope of both the enamide synthesis itself, and of the synthetic applications of the enamide products. These objectives are at the heart of this proposal.