Structure-Reactivity Relationship for Organic Small Molecule-Metal Complexes

本课题旨在建立有机小分子过渡金属配合物的结构-反应性关系，并将这种关系应用于选择性有机合成。1)烯丙基配合物的立体化学控制。通过与双金属基团的配位，建立了1-取代烯丙基配体具有不同寻常的抗体化学反应的要求。利用双（恶唑啉）配体实现了这些配体与Pd的对映选择性配位。2)三甲基乙烷配体及其类似物的结构与反应性。三甲基乙烷-钯中间体是由2-斯坦基甲基allypalladium配合物与醛以正式的[2+3]环化方式发生去氨化反应生成的。制备了类似的氧三甲基烯乙二钯配合物，并对其结构进行了x射线分析。这些配合物通过[1+2]环加成与降冰片烯反应。3)烯丙基、丙炔和丁二烯双金属配合物的合成与结构。本文提出了用有机钯（II）配合物与钯(0)配合物反应制备丙烯基、丙炔和丁二烯钯-钯配合物的一般方法。x射线结构分析揭示了一个由有机小配体桥接的Pd_2X结构特征。

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.