Metal Mediated and Catalyzed Organic Synthetic Methods

这项建议的目的是开发和应用新的有机化学合成方法，基于过渡金属物种催化的有机反应。这笔赠款中提议的项目建立在我们之前发现赠款的发展基础上，但又探索了新的方向。正在研究的个别方法的核心是过渡金属单元通过稳定中间体或稳定在没有过渡金属单元的情况下无法存在的产物，通过正常的合成方法使可能的转化困难或不可能发生的能力，特别是对炔烃-二氧化碳(CO)6单元的关注。重点关注的具体过程将来自这个单元稳定带正电的(碳阳离子)物种的能力，以及使含有环的化合物中的三键物种稳定的能力。此外，我们打算研究乙炔-二氧化碳(CO)6单元对带有未配对电子(自由基)的中间体的影响，以及钴单元的存在是否使这些中间体在合成中更有用。还将探索正在研究的化学的潜在机制方面。最终的目的是，化学将发展到很好地理解化学参数的程度，并将进行选定目标化合物的合成，以向人们展示该方法的实用性，并制造在合成方面鲜有人注意的自然发生的化合物。

The purpose of this proposal is the development and application of new organic chemistry synthetic methods, based on organic reactions mediated by transition metal species. The projects proposed in this grant build upon the developments of our previous Discovery Grant and yet investigate new directions. Central to the individual methods under study is the ability of the transition metal unit to make possible transformations either difficult or impossible by normal synthetic methods, by either stabilizing intermediates or by stabilizing products that could not exist in the absence of the transition metal unit, with particular focus on the alkyne-Co2(CO)6 unit. The specific processes focused on will come from the ability of this unit to stabilize positively charged (carbocation) species, and the ability to make triple bond species in ring containing compounds stable. In addition, we intend to study the effects of the alkyne-Co2(CO)6 unit on intermediates with unpaired electrons (radicals), and whether these intermediates are made more useful in synthesis by the presence of the cobalt unit. The underlying mechanistic aspects of the chemistry under study will also be explored. It is ultimately intended that the chemistry will developed to the point where the parameters of the chemistry is well understood, and the  the synthesis of selected target compounds will be undertaken, to demonstrate to utility of the method and to make naturally occurring compounds that have seen little attention in terms of synthesis.