Pyridine adducts of chiral arene ruthenium compounds. Diastereoselective synthesis and characterization

被引:19
作者
Faller, JW [1 ]
Grimmond, BJ [1 ]
Curtis, M [1 ]
机构
[1] Yale Univ, Dept Chem, New Haven, CT 06520 USA
关键词
D O I
10.1021/om000319s
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The compounds [CyRu(eta (2)-Ph2PCH(Me)Ph2PO)L] [SbF6](2), where Cy = p-CH3C6H4CH(CH3)(2); L = pyridine, 2; 3,5-lutidine, 3; isoquinoline, 4, were synthesized by chloride abstraction from [CyRu(eta (2)-Ph2PCH(Me)Ph2PO)Cl] [SbF6], 1, followed by treatment of the intermediate Lewis acid [CyRu(eta (2)-Ph2PCH(Me)Ph2PO)][SbF6](2) with the appropriate ligand. Characterization by elemental analysis, H-1, P-31(H-1), VT NMR spectroscopy, and IR spectroscopy indicated that 2-4 were obtained as a mixture of exo and endo diastereomers (de = 14-60%). The endo diastereomer of compound 2 was also characterized by X-ray crystallography which revealed the (R-Ru*,R-C*) relative configuration of the two stereogenic centers within the molecule. In contrast to analogues with other neutral donors, P-31{H-1} NMR spectroscopy experiments demonstrated that 2-4 were stable to diastereomer interconversion in solution. This suggests that epimerization of the ruthenium center in an intermediate exo-[CyRu(eta (2)-Ph2PCH(Me)Ph2PO)] [SbF6](2) occurred by a path unavailable to 2-4 by inversion of the Ru(eta (2)-Ph2PCH(Me)Ph2PO) ring.
引用
收藏
页码:5174 / 5181
页数:8
相关论文
共 50 条
[1]   SIR92 - a program for automatic solution of crystal structures by direct methods [J].
ALTOMARE, A ;
CASCARANO, G ;
GIACOVAZZO, G ;
GUAGLIARDI, A ;
BURLA, MC ;
POLIDORI, G ;
CAMALLI, M .
JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1994, 27 :435-435
[2]   Intriguing coordination behaviors of aquo and amine ligands bound to the organoruthenium(II) cation [Ru(eta(6)-C6H6)(bpop)](2+) (bpop=2,2-bis[4(R)-phenyl-1,3-oxazolon-2-yl]propane) [J].
Asano, H ;
Katayama, K ;
Kurosawa, H .
INORGANIC CHEMISTRY, 1996, 35 (20) :5760-&
[3]   COORDINATION CHEMISTRY AND CATALYSIS WITH HEMILABILE OXYGEN PHOSPHORUS LIGANDS [J].
BADER, A ;
LINDNER, E .
COORDINATION CHEMISTRY REVIEWS, 1991, 108 (01) :27-110
[4]   (ETA-6-HEXAMETHYLBENZENE)RUTHENIUM COMPLEXES [J].
BENNETT, MA ;
HUANG, TN ;
MATHESON, TW ;
SMITH, AK .
INORGANIC SYNTHESES, 1982, 21 :74-78
[5]  
Brunner H, 1999, ANGEW CHEM INT EDIT, V38, P1195, DOI 10.1002/(SICI)1521-3773(19990503)38:9<1194::AID-ANIE1194>3.0.CO
[6]  
2-X
[7]  
Brunner H., 1980, ADV ORGANOMET CHEM, V18, P151
[8]   Chiral ruthenium complexes as catalysts in enantioselective Diels-Alder reactions. Crystal structure of the Lewis acid dienophile adduct [J].
Carmona, D ;
Cativiela, C ;
Elipe, S ;
Lahoz, FJ ;
Lamata, MP ;
Pilar, M ;
de Viu, LR ;
Oro, LA ;
Vega, C ;
Viguri, F .
CHEMICAL COMMUNICATIONS, 1997, (24) :2351-2352
[9]   PALLADIUM(II) AND PLATINUM(II) COMPLEXES WITH CHELATING SULFINYL FUNCTIONS [J].
CHOOI, SYM ;
LEUNG, PH ;
MOK, KF .
INORGANICA CHIMICA ACTA, 1993, 205 (02) :245-247
[10]   SELECTIVE ACTIVATION OF ONE METHYL KETONE ENANTIOFACE VIA SIGMA-BINDING TO A CHIRAL TRANSITION-METAL TEMPLATE - SYNTHESIS, STRUCTURE, AND REACTIVITY OF RHENIUM KETONE COMPLEXES [(ETA-5-C5H5)RE(NO)(PPH3)(ETA-1-O=C(CH3)R)]+X- [J].
DALTON, DM ;
FERNANDEZ, JM ;
EMERSON, K ;
LARSEN, RD ;
ARIF, AM ;
GLADYSZ, JA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (25) :9198-9212