Structure-Reactivity Relationship for Organic Small Molecule-Metal Complexes

本研究的目的是建立有机小分子-过渡金属配合物的结构-反应性关系，并将其应用于选择性有机合成。1）π-烯丙基配合物的立体化学控制。1-取代的烯丙基配体承担不寻常的反立体化学的要求已经通过它们与双金属部分的配位而建立。利用双恶唑啉配体实现了这些配体与钯的对映选择性配位。2）三亚甲基甲烷配体及其类似物的结构和反应性。通过2-锡烷基甲基烯丙基钯配合物的脱锡反应，与醛类化合物发生[2+3]环化反应，生成三亚甲基甲烷钯中间体。合成了类似的氧代三亚甲基甲烷钯配合物，并用X射线衍射分析了它们的结构。3）μ-烯丙基、μ-炔丙基和μ-丁二烯双金属配合物的合成与结构。本文发展了一种制备μ-烯丙基、μ-炔丙基和μ-丁二烯Pd-Pd配合物的通用方法，该方法包括有机钯（II）配合物与Pd（0）配合物反应。X-射线衍射分析表明，Pd_2X骨架是由有机小分子配体桥联而成。

The objective of this research project is to establish structure-reactivity relationship in organic small molecule-transition metal complexes, and to apply such relation to selective organic synthesis.1) Stereochemical control of pi-allylic complexes. Requirements for 1-substituted allyl ligands to assume unusual anti-sterochemistry have been established by means of their coordination to dimetallic moieties. Enantioselective coordination of these ligands to Pd was realized by the use of bis(oxazoline) ligand.2) Structure and reactivity of trimethylenemethane ligand and its analogs. Trimethylenemethane-palladium intermediate has been generated by means of destannylation of 2-stannylmethylallypalladium complexes, which reacted with aldehydes in a formal [2+3] cyclization manner. Analogous oxotrimethylenemethanepalladium complexes have been prepared, and their structure revealed by X-ray analysis. These complexes reacted with norbornene via [1+2] cycloadditon.3) Synthesis and structure of mu-Allyl, mu-Propargyl and mu-butadiene dimetallic complexes. A general method for obtaining mu-allyl, mu-propargyl and mu-butadiene Pd-Pd complexes has been developed, which consists of reacting organopalladium(II) complexes with Pd(0) complexes. X-ray structure analysis revealed a characteristic Pd_2X framework which is bridged by organic small ligands.