Transmetalations Mediated By Organocopper Reagents

这项研究由有机合成计划资助。 Lipshutz博士将继续他非常富有成效的研究， 基于铜络合物的有机金属试剂。 这些 具有生产高选择性合成 可用于合成反应性的 在自然界中发现的分子。 这项研究部分描述了一些新的合成 这些方法利用了 更高阶的基于铜的金属转移过程， 有机锡化合物 耐受各种功能性 将研究锡烷前体本身内的基团， 希望形成高度官能化的铜酸盐。 烯丙基 试剂应在以下条件下进行置换检查： 四面体和三角中心。 此外，循环 烯丙基锡烷被认为是烯丙基的化学， 在一氧化碳存在的情况下， α，β-不饱和酮的1，4-酰化。 作为多烯建筑项目的一部分， 将利用选址优势， 由于相对汇率的不同而使金属转移成为可能 在乙烯基锡烷之间。 应用于合成问题 将指出白三烯和信息素区域。 的 使用高级氧化“分解”的可能性 铜酸盐，在合成意义上，实现联芳基偶联将 也被研究。 研究的最后一部分涉及光谱学 几个物种的调查。 一个是关于 由CuI/LiCl/Bu 3SnH衍生的新试剂，被认为是 （X）HCuLi。 另一个将是深入研究山本的 试剂.

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.