Synthesis, Properties and Chemical Functions of Group 8 Transition Metal Nitrosyl Complexes

本课题的研究目的是利用新合成的络合物的特性来开发新的合成反应。特别强调了ETA^3-烯丙基亚硝基络合物的化学。1.由烯丙基卤化物合成了(ETA^3-1-三甲基硅氧基烯丙基)Fe(CO)_2NO配合物1，从α，β-不饱和羰基化合物合成了(ETA^3-1-三甲基硅氧烯丙基)Fe(CO)_2NO配合物2，从α-卤代羰基化合物合成了(ETA^3-2-三甲基硅氧烯丙基)Fe(CO)_2NO配合物3，从1，3-二烯合成了[ETA^3-1-(酰甲基)-烯丙基]Fe(CO)_2NO配合物4，和(ETA^3-1-乙氧基烯丙基)Fe(CO)_2NO络合物5，以Bu_4N^+[Fe(CO)_3NO]^-为试剂。2.所有这些配合物都能与碳亲电体和碳亲核体反应，具有很高的区域选择性。3.这些络合物表现出有趣的反应性特征。详细的研究表明，化合物1可作为烯丙基阳离子和烯丙基阴离子的合成等价体，化合物2可作为β-酰基碳正离子和β-酰基碳负离子的合成体，配合物3可作为α-酰基碳正离子和α-酰基碳负离子的合成体，配合物4可作为1，3-二烯1，4-官能化的中间体，而配合物5可作为合成多官能团醇的中间体。4.1，2，3和4的烯丙基配体与α，β-不饱和羰基化合物发生共轭加成反应，得到了多种具有高选择性的多官能团化合物。5.铁配合物与碳亲电体和碳亲核体的反应通过两个不同的、不同的立体化学过程进行，这两个反应的区域和立体选择性一般都很高。

The title subjects have been studied with the intention of developing new synthetic reactions by utilizing characteristic chemical properties of newly synthesized complexes. The special emphasis has been placed on the chemistry of eta^3-allylnitrosyliron complexes. The major outcomes of this research can be summarized as follows :1. (eta^3-Allyl)Fe(CO)_2NO complexes 1 can be synthesized efficiently from allylic halides, (eta^3-1-trimethylsiloxyallyl)Fe(CO)_2NO complexes 2 from alpha, beta-unsaturated carbonyl compounds, (eta^3-2-trimethylsiloxyallyl)Fe(CO)_2NO complexes 3 from alpha-halocarbonyl compounds, [eta^3-1-(acylmethyl)-allyl]Fe(CO)_2NO complexes 4 from 1, 3-dienes, and (eta^3-1-acetoxyallyl)Fe(CO)_2NO complexes 5 from alkenyloxiranes by using Bu_4N^+[Fe(CO)_3NO]^- as a reagent. 2. All these complexes react with both of carbon electrophiles and carbon nucleophiles with a high regio-selectivity. 3. These complexes exhibit interesting reactivity features. The detailed studies have shown that the complexes 1 can be utilized as synthetically equivalent synthons for both of allylcations and allylanions, the complexes 2 as those for both of beta-acylcarbocations and beta-acylcarbanions, the complexes 3 as those for both of alpha-acylcarbocations and alpha-acylcarbanions, the complexes 4 as intermediates for 1, 4-functionalization of 1, 3-dienes, and the complexes 5 as intermediates for the synthesis of multifunctionalized alcohols. 4. The allylic ligands of 1, 2, 3, and 4 undergo a conjugate addition to alpha, beta-unsaturated carbonyl compounds, affording a variety of multifunctionalized compounds with a high selectivity. 5. The reactions of the iron complexes with carbon electrophiles and carbon nucleophiles proceed via two different, distinctive stereochemical courses, and the regio- and stereo-selectivities of both the reactions are generally high.