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Introduction of Heteroatoms Based on New Catalyst Activities of Lanthanide Complexes

基于稀土配合物新催化活性引入杂原子

基本信息

批准号：
13650923
负责人：
TAKAKI Ken
金额：
$ 2.3万
依托单位：
HIROSHIMA UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2002
项目状态：
已结题

项目摘要

1. Hydrosilylation of Olefins and Dehydrogenative Double Silylation of Conjugated Dienes Catalyzed by Lanthanide Amide Complexes.Lanthanide-imine complex, [Yb(η^2-ph_2CNPh)(hmpa)_3] (1), and diamide complexes, prepared from 1 and equimolar amounts of Ph_2NH, catalyzed hydrosilylation of olefins with PhSiH_3 and Ph_2SiH_2 very effectively. On the other hand, the catalysts induced dehydrogenative double silylation of conjugated dienes to give selectively 1,4-bis(silyl)-2-butenes instead of expected 1,4- and 1,2-hydrosilylation products. It has been found that hydride and silyl species, [Yb[-H and [Yb]-Si, are generated together from the catalysts and hydrosilanes and that the former reacts with the olefins and the latter with the dienes predominantly.2. Hydrophosphination of Alkynes and Related Carbon-Carbon Multiple Bonds Catalyzed by Lanthanide-Imine Complexes.Intermolecular hydrophosphination of alkynes with diphenylphosphine is catalyzed by a Yb-imine complex 1 to give alkenylphosphines and phosphine oxides after oxidative workup in good yields under mild conditions. This reaction is also applicable to various carbon-carbon multiple bonds such as conjugated diynes and dienes, allenes, and styrene derivatives. Region- and stereoselectivity, and the scope and limitation of the present reaction clearly differ from those of the corresponding radical reaction. Instead, the reaction takes place through insertion of alkynes to a Yb-PPh_2 species, followed by protonation. In fact, the Yb-phosphide complex, [Yb(PPh_2)_2(hmpa)_3], is obtained from the imine complex and phosphine, which exhibits similar catalyst activity for the hydrophosphination. The empirical rate law is v=k [catalyst]^2[alkynes]^1[phosphine]^0 at least under the standard conditions.

1. 稀土酰胺配合物催化的烯烃氢化硅烷化和共轭二烯的脱氢双硅烷化。稀土-亚胺配合物，[Yb(η^2-ph_2CNPh)(hmpa)_3] (1)，和二酰胺配合物，由 1 和等摩尔量的 Ph_2NH 制备，催化氢化硅烷化与PhSiH_3和Ph_2SiH_2的烯烃非常有效。另一方面，催化剂诱导共轭二烯脱氢双硅烷化，选择性地产生1,4-双(甲硅烷基)-2-丁烯，而不是预期的1,4-和1,2-氢化硅烷化产物。研究发现，催化剂和含氢硅烷共同生成氢化物和甲硅烷基物质[Yb[-H和[Yb]-Si]，并且前者主要与烯烃反应，后者主要与二烯反应。2．稀土-亚胺络合物催化炔烃及相关碳-碳多重键的氢膦化。Yb-亚胺络合物 1 催化炔烃与二苯基膦的分子间氢膦化，在温和条件下进行氧化处理后，以良好的收率得到烯基膦和氧化膦。该反应也适用于各种碳-碳多重键，例如共轭二炔和二烯、丙二烯和苯乙烯衍生物。本反应的区域选择性和立体选择性以及范围和限制明显不同于相应的自由基反应。相反，该反应是通过将炔插入 Yb-PPh_2 物质中，然后进行质子化来发生的。事实上，Yb-磷化物配合物[Yb(PPh_2)_2(hmpa)_3]是由亚胺配合物和膦得到的，其对氢膦化反应表现出类似的催化剂活性。经验速率定律至少在标准条件下为 v=k [催化剂]^2[炔烃]^1[膦]^0。