Transmetalations Mediated By Organocopper Reagents

这项研究是由有机合成计划资助的。Lipshutz博士将继续他在铜络合物基础上的有机金属试剂的卓有成效的研究。这些有可能产生高选择性的合成工具，可用于合成自然界中发现的反应性分子。本研究在一定程度上描述了一些新的合成方法，这些方法利用了有机锡化合物的高阶铜基金属转化过程的效率和温和性。将研究锡烷前驱体本身对各种官能团的耐受性，寻求形成高官能团的铜酸盐。烯丙基试剂在四面体中心和三角中心的取代都要进行检验。此外，还考虑了环烯丙基锡烷，以及铜酸烯丙基在一氧化碳存在的情况下直接向α， β -不饱和酮的1,4-酰基化的化学反应。作为多烯结构计划的一部分，将开发新的关键元件，这些关键元件将利用乙烯锡烷之间相对速率的差异而实现的位点选择性金属转化。并指出在白三烯和信息素合成领域的应用问题。还将研究在合成意义上利用高阶铜酸盐的氧化“分解”来影响联芳基偶联的可能性。研究的最后一部分包括对几个物种的光谱调查。一个是关于由CuI/LiCl/Bu3SnH衍生的新试剂的性质，被认为是(X)HCuLi。另一个将是对山本试剂的深入研究。

This research is being funded by the Organic Synthesis Program. Dr. Lipshutz will continue his very productive studies of organometallic reagents based upon complexes of copper. These have the potential for producing highly selective synthetic tools that can be used in the synthesis of the reactive molecules that are found in nature. This research describes, in part, a number of new synthetic methods which take advantage of the efficiency and mildness of higher order cuprate-based transmetalation processes of organotin compounds. Tolerance to a variety of functional groups within the stannane precursor itself will be studied, looking to form highly functionalized cuprates. Allylic reagents are to be examined with respect to substitutions at both tetrahedral and trigonal centers. Moreover, cyclic allylic stannanes are considered, as is the chemistry of allyl cuprates in the presence of carbon monoxide en route to direct 1,4-acylations of alpha,beta-unsaturated ketones. As part of a program in polyene construction, new lynchpins will be developed which will take advantage of site-selective transmetalations made possible by differences in relative rates between vinylstannanes. Applications to synthetic problems in the leukotriene and pheromone areas will be pointed out. The possibility of using oxidative "decomposition" of higher order cuprates, in a synthetic sense, to effect biaryl couplings will also be studied. The last portion of the research involves spectroscopic investigations of several species. One concerns the nature of the new reagent derived from CuI/LiCl/Bu3SnH, believed to be (X)HCuLi. Another will be an in-depth study of Yamamoto's reagent.