C-N and C-C coupling reactions:: Preparation of new N-heterocyclic ruthenium derivatives

被引:45
作者
Buil, ML [1 ]
Esteruelas, MA [1 ]
López, AM [1 ]
Oñate, E [1 ]
机构
[1] Univ Zaragoza, CSIC, Inst Ciencia Mat Aragon, Dept Quim Inorgan, E-50009 Zaragoza, Spain
关键词
D O I
10.1021/om020652r
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Three novel types of complexes containing heterocyclic ligands are prepared by condensation of the allenylidene ligand of [Ru(eta(5)-C5H5)(=C=C=CPh2)(CO)((PPr3)-Pr-i)]BF4 (1) With propargylamines. Complex 1 reacts with propargylamine to give initially [Ru(eta(5)-C5H5)-{C(CH=CPh2)=NHCH(2)Cequivalent toCH}(CO)((PPr3)-Pr-i)]BF4 (2). Treatment of 2 with KOH in methanol affords the bicyclic derivative Ru(eta(5)-C5H5){4-methylidene-6,6-diphenyl-2-azabicyclo[3.1.0]-hex-2-en-1-yl}(CO)((PPr3)-Pr-i) (3). The formation of 3 takes place via the intermediate Ru(eta(5)-C5H5){C(CH=CPh2)=NCH(2)Cequivalent toCH}(CO)((PPr3)-Pr-i) (4), which is isolated when the deprotonation of 2 is carried out in tetrahydrofuran as solvent. In contrast to propargylamine, the addition of 1,1-diethylpropargylamine to 1 leads to the dihydropyridiniumyl derivative [Ru(eta(5)-C5H5)-{2,2-diethyl-5-diphenylidene-2,5-dihydropyridinium-6-yl)(CO)((PPr3)-Pr-i)]BF4 (5) in a one-pot synthesis. Complex 1 also reacts with N-methylpropargylamine. The reaction affords [Ru-(eta(5)-C5H5){C(CH=CPh2)=N(CH3)CH(2)Cequivalent toCH}(CO)((PPr3)-Pr-i)]BF4 (6). Treatment of 6 with sodium methoxide, at -78 degreesC, gives a 1:1 mixture of the dihydronaphthopyrrolyl diastereomers (RRuSC,SRuRC)-[Ru(eta(5)-C5H5){9-phenyl-4,4a-dihydronaphtho[2,3-c]-1-pyrrolyl})(CO)((PPr3)-Pr-i) (7a) and (RRuRC,SRuSC)-[Ru(eta(5)-C5H5){9-phenyl-4,4a-dihydronaphtho[2,3-c]-1-pyrrolyl})(CO)((PPr3)-Pr-i) (7b). Complexes 3 and 5 and the enantiomeric mixture 7a have been characterized by X-ray diffraction analysis.
引用
收藏
页码:162 / 171
页数:10
相关论文
共 50 条
[1]  
[Anonymous], 1997, SHELXS 86 SHELXL 97
[2]  
Aumann R, 2000, EUR J ORG CHEM, V2000, P17, DOI 10.1002/(SICI)1099-0690(200001)2000:1<17::AID-EJOC17>3.0.CO
[3]  
2-T
[4]   Formal [4+3], [4+2], [4+1] and [2+1] cycloadditions and acid-base reaction of 2-methyl-1,3-dimorpholino-1,3-butadiene with Fischer carbene complexes [J].
Barluenga, J ;
Aznar, F ;
Fernandez, M .
CHEMISTRY-A EUROPEAN JOURNAL, 1997, 3 (10) :1629-1637
[5]   Diastereoselective intermolecular cyclopropanation of simple alkenes by fischer alkenyl and heteroaryl carbene complexes of chromium:: Scope and limitations [J].
Barluenga, J ;
López, S ;
Trabanco, AA ;
Fernández-Acebes, A ;
Flórez, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (34) :8145-8154
[6]   Regioselective addition of dienes to the Cβ-Cγ double bond of the allenylidene ligand of [Ru(η5-C5H5)(=C=C=CPh2)(CO)(PiPr3)]BF4 [J].
Baya, M ;
Buil, ML ;
Esteruelas, MA ;
López, AM ;
Oñate, E ;
Rodríguez, JR .
ORGANOMETALLICS, 2002, 21 (09) :1841-1848
[7]   Synthesis and characterization of hydride-alkynyl, allenylidene, carbyne, and functionalized-alkynyl complexes containing the [Os(η5-C5H5) (PiPr3)-2]+ fragment:: The complex [Os(η5-C5H5)(C=C=CPh2)(PiPr3)2]PF6, a new type of allenylidene derivative from the reactivity point of view [J].
Baya, M ;
Crochet, P ;
Esteruelas, MA ;
Gutiérrez-Puebla, E ;
López, AM ;
Modrego, J ;
Oñate, E ;
Vela, N .
ORGANOMETALLICS, 2000, 19 (13) :2585-2596
[8]  
BERKE H, 1981, Z NATURFORSCH B, V36, P1277
[9]   Addition of secondary and primary amines to the allenylidene ligand of [Ru(η5-C5H5)(C=C=CPh2) (CO)(PiPr3)]BF4:: Synthesis of azoniabutadienyl, aminoallenyl, and azabutadienyl derivatives of ruthenium(II) [J].
Bernad, DJ ;
Esteruelas, MA ;
López, AM ;
Modrego, J ;
Puerta, MC ;
Valerga, P .
ORGANOMETALLICS, 1999, 18 (24) :4995-5003
[10]   The allenylidene complex [Ru(η5-C5H5)(C=C=CPh2) (CO)(PiPr3)]BF4 as a precursor of novel pyrido[1,2-a]pyrimidinyl and 1,3,-thiazinyl complexes [J].
Bernad, DJ ;
Esteruelas, MA ;
López, AM ;
Oliván, M ;
Oñate, E ;
Puerta, MC ;
Valerga, P .
ORGANOMETALLICS, 2000, 19 (21) :4327-4335