Transmetalations Mediated By Organocopper Reagents

这项研究是由有机合成计划资助的。利普舒茨博士将继续他对以铜的络合物为基础的有机金属试剂的非常有成效的研究。它们有可能生产高度选择性的合成工具，可用于合成自然界中发现的活性分子。这项研究部分描述了一些新的合成方法，这些方法利用了基于高阶铜酸盐的有机锡化合物转金属反应的效率和温和的优点。将研究锡烷前体本身对各种官能团的耐受性，以期形成高度官能化的铜酸盐。关于四面体和三角中心的取代，要检查烯丙基试剂。此外，还考虑了环烯丙基锡烷，以及在一氧化碳存在下烯丙基铜酸盐在α，β-不饱和酮直接1，4-酰化反应中的化学。作为多烯建造计划的一部分，将开发新的衬销，它将利用乙烯基锡烷之间相对速率的差异而实现的位置选择性转金属。将指出其在白三烯和信息素领域的合成问题上的应用。还将研究在合成意义上利用高阶铜酸盐的氧化“分解”来实现联芳基偶联的可能性。研究的最后一部分涉及对几个物种的光谱调查。一种是关于CuI/LiCl/Bu3SnH衍生的新试剂的性质，据信是(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.