摘要
利用2,3-二(二苯膦氧基)-1,3-丁二烯与胺的迈克尔加成反应,合成了单胺基及环胺基改性的有机氧化膦,经有机硅烷还原,制备出胺基取代的膦配体,所得化合物经NMR及单晶X射线衍射分析.考察了所得配体与Ru(PPh3)3Cl2组成的催化体系在苯乙酮氢转移反应中的催化活性,发现氧化膦与Ru原位形成的催化剂比其还原态的三价膦组成的催化剂催化活性还高,二胺基取代的二氧化膦配体具有较高的催化活性,TON可达273.而采用先制备催化剂再催化反应时配体6的钌络合物催化活性TON可达352.
A series of mono and cyclic amines modified by phosphine oxides have been synthesized by Michael addition reaction of 2,3-bis（diphenylphosphinyl）-1,3-butadiene with amine.Then the phosphine oxide was reduced by silane to give amine modified by phosphine.The obtained compounds were characterized by NMR and X-ray diffraction.The activity of catalyst system formed in situ of modified phosphine ligands with Ru（PPh3）3Cl2 in catalytic hydrogen transfer reaction of acetophenone was evaluated.It is found that the activity of catalyst formed by mixture of phosphine oxide and Ru is higher than that of phosphine and Ru.The catalyst of Ru with bis-amino substituted diphosphine oxide ligands has high catalytic activity and its TON is up to 273.While the activity（TON） of Ru complex with ligand 6 which prepared before the catalytic reaction,can be further improved up to 352.
出处
《有机化学》
SCIE
CAS
CSCD
北大核心
2011年第9期1406-1410,共5页
Chinese Journal of Organic Chemistry
基金
国家自然科学基金(No.20674015)资助项目
关键词
氧化膦
迈克尔加成
膦氮配体
钌催化剂
氢转移反应
phosphine oxide
Michael addition
P-N ligand
ruthenium catalyst
hydrogen transfer reaction
