Selective C-H Bond Activation by Group 7 and 8 Transition Metal Complexes and its Application to Organic Synthesis

7族和8族过渡金属配合物的选择性C-H键活化及其在有机合成中的应用

基本信息

批准号：
03453099
负责人：
KOMIYA Sanshiro
金额：
$ 4.16万
依托单位：
Tokyo University of Agriculture and Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1991
资助国家：
日本
起止时间：
1991 至 1992
项目状态：
已结题

项目摘要

The objects of this research are development of novel C-H bond activation of functionalized organic substances using group 7 and 8 transition metal complexes and its application to selective organic syntheses. In this research, new rhenium, iron, and ruthenium complexes, which can smoothly produce reactive coordinatively unsaturated species, are successfully prepared. They are ReH(C_2H_4)_2(PMe_2Ph)_3 (1), ReH(N_2)(PMe_2Ph)_4 (2), [MnMe_2(dmpe)_2]^+[AlMe_4]^- (3), [MnMe_2(dmpe)_2]^+[BPh_4]^- (4), RuH_2(PPh_3)_4 (5), Ru(C_2H_4)(PPh_3)_3 (6), Fe(N_2)(depe)_2 (7), Complexes 2,5, and 6 react with active hydrogen compounds to give hydride complexes having an enolate anionic ligand. Enolate complexes derived from alpha-cyanocarboxylates have direct coordination of the cyano group to the metal leaving a highly nucleophlic enolate moiety. These complexes smoothly react with aldehydes and acrylonitrile to give aldol reaction and Michael addition products respectively. In contrast, enolate compl … More exes, which are produced by the reaction of 5 and 6 with 2,4- pentanedione, do not react with these compounds. All these complexes 2,5,6 and the enolate complexes thus prepared as well as Ru(cod)(cot)/PR_3 system act as selective catalysts of these reactions. These results indicate that the enolate complexes isolated in this research are active reaction intermediates, and support the unusually high selectivity of the ruthenium and rhenium catalyzed aldol and Michael type reactions.On the other hand, the C-H bonds of alkenecarboxylates oxidatively add selectively to ruthenium(0) to give new hydridoalkenyl and hydrido-pi-allyl type complexes, depending on the esters employed. In the latter case, dienecarboxylate type complexes are gradually formed by the beta-hydrogen elimination from a sigma-allyl intermediate. The regeiselectivity in these CH bond activation reactions can be understood by the thermodydamic stability of the ruthenim products.Unusual olefin metathesis reaction between coordinated alpha-cyanocinnamate on rhenium and tetracyanoethylene takes place under ambient conditions. The reaction is considered as the first example of olefin metathesis of functionalized olefins. Less

这项研究的对象是使用第7和8组的过渡金属配合物及其在选择性有机合成中的应用的新型C-H键激活的新型C-H键激活。在这项研究中，可以成功制备新的rhenium，铁和芳族复合物，它们可以平稳地产生反应性的不饱和物种。它们是REH（C_2H_4）_2（PME_2PH）_3（1），REH（N_2）（PME_2PH）_4（2），[Mnme_2（dmpe）_2] _2]^+[Alme_4]^ - （3） RUH_2（PPH_3）_4（5），RU（C_2H_4）（PPH_3）_3（6），Fe（N_2）（N_2）（DEPE）_2（7），复合物2,5，6和6与活性氢化合物反应，使氢配合物具有富含烯烃的含有阴离子的氢配合物。源自α-氰基羧酸盐的烯丙基络合物具有氰基团直接配位到金属上，留下了高度核磷酸的部分。这些复合物与醛和丙烯酸酯菌平滑反应，分别产生醛醇反应和迈克尔添加产物。相比之下，烯醇浓度……更多的exes是由5和6与2,4-戊二酮的反应产生的，不会与这些化合物反应。所有这些配合物2,5,6和因此制备的烯烃复合物以及RU（COD）/PR_3系统作为这些反应的选择性催化剂的作用。 These results indicate that the enolate complexes isolated in this research are active reaction intermediates, and support the unusually high selectivity of the ruthenium and rhenium catalyzed aldol and Michael type reactions.On the other hand, the C-H bonds of alkenecarboxylates oxidatively add selectively to ruthenium(0) to give new hydridalkenyl and hydrido-pi-allyl type complexes, depending on the esters Employed.在后一种情况下，二甲基二羧酸盐型复合物逐渐由Sigma-Alyl中级消除β-氢化剂形成。这些CH键激活反应中的regeeelectivity可以通过Ruthenim产品的热稳定性来理解。在环境条件下发生。该反应被认为是功能化烯烃的烯烃分解的第一个例子。较少的