NOVEL CONCEPTS IN DIRECTED BIARYL SYNTHESIS .39. THE INFLUENCE OF ALUMINUM TRICHLORIDE ON A CONFIGURATIVELY LABILE LACTONE-BRIDGED BIARYL - QUANTUM-CHEMICAL CALCULATIONS AND OPTICAL SPECTROSCOPY

被引:11
作者
BRINGMANN, G [1 ]
DAUER, U [1 ]
SCHUPP, O [1 ]
LANKERS, M [1 ]
POPP, J [1 ]
POSSET, U [1 ]
WEIPPERT, A [1 ]
KIEFER, W [1 ]
机构
[1] UNIV WURZBURG,INST PHYS CHEM,D-97070 WURZBURG,GERMANY
关键词
QUANTUM CHEMICAL CALCULATIONS; OPTICAL SPECTROSCOPY; ALUMINUM COMPLEXES; LACTONE COMPLEXES; BENZONAPHTHOPYRANONE;
D O I
10.1016/0020-1693(94)03915-1
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Semiempirical and ab initio calculations on the binding properties of the AlCl3 complex of 1,3-dimethylbenzo[b]naphtho[1,2-d]pyran-6-one are reported. Compounds of this type are key intermediates in the stereoselective synthesis of axially chiral biaryl systems. Semiempirical (MNDO, PM3) and ab initio (STO-3G, 3-21G) calculations give important information about conformational changes that occur by complexing the free lactone with AlCl3: the calculations predict a significant influence on the lengths of the (C=O)exo and (C-O)endo bonds, and a distinct planarization of the heterocyclic lactone part of the complexed benzonaphthopyranone. IR and Raman spectroscopy was applied in order to confirm the theoretical predictions. The good agreement of results obtained by semiempirical frequency calculations with the experimental data supports the assignment of vibrational bands affected on coordination. The highest shift caused by coordination (- 152 cm-1) is observed for nu(C=O).
引用
收藏
页码:247 / 253
页数:7
相关论文
共 29 条
[1]   AN ALGORITHM FOR GEOMETRY OPTIMIZATION WITHOUT ANALYTICAL GRADIENTS [J].
BAKER, J .
JOURNAL OF COMPUTATIONAL CHEMISTRY, 1987, 8 (05) :563-574
[2]  
BRINGMANN G, 1994, LIEBIGS ANN CHEM, P439
[3]   NOVEL CONCEPTS IN DIRECTED BIARYL SYNTHESIS .15. CHIRAL RHENIUM COMPLEXES [(ETA-5-C5H5)RE(NO)(PPH3)(R,R-LACTONE)]+BF4- OF LACTONE-BRIDGED BIARYLS AS LIGANDS - SYNTHESIS, STRUCTURE, AND STEREOCHEMICAL PROPERTIES [J].
BRINGMANN, G ;
SCHUPP, O ;
PETERS, K ;
WALZ, L ;
VONSCHNERING, HG .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1992, 438 (1-2) :117-130
[4]   ATROPO-ENANTIOSELECTIVE BIARYL SYNTHESIS BY STEREOCONTROLLED CLEAVAGE OF CONFIGURATIVELY LABILE LACTONE-BRIDGED PRECURSORS USING CHIRAL H-NUCLEOPHILES [J].
BRINGMANN, G ;
HARTUNG, T .
TETRAHEDRON, 1993, 49 (36) :7891-7902
[5]  
BRINGMANN G, 1992, LIEBIGS ANN CHEM, P225
[6]   THE DIRECTED SYNTHESIS OF BIARYL COMPOUNDS - MODERN CONCEPTS AND STRATEGIES [J].
BRINGMANN, G ;
WALTER, R ;
WEIRICH, R .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1990, 29 (09) :977-991
[7]  
BRINGMANN G, 1991, SYNLETT, P581
[8]  
BRINGMANN G, 1992, SELECTIVE REACTIONS, P183
[9]  
BRINGMANN G, 1993, GIT FACHZ LAB, V3, P189
[10]  
Bringmann G., 1990, ANGEW CHEM, V102, P1006