SYNTHESIS AND DYNAMIC BEHAVIOR OF (1,5)CYCLOOCTATETRAENOPHANES - EFFECT OF DISTAL ATOM BRIDGING ON RACEMIZATION RATES AND ELECTROCHEMICAL REDUCIBILITY

被引:32
作者
PAQUETTE, LA
TROVA, MP
LUO, JM
CLOUGH, AE
ANDERSON, LB
机构
[1] The Department of Chemistry, The Ohio State University, Columbus
关键词
D O I
10.1021/ja00157a037
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The [5]-, [6]-, [8]-, and [10](1,5)cyclooctatetraenophanes as well as non-C2-symmetric methyl homologues of these 1,5-bridged [SJannulenes have been prepared conveniently via a route that holds promise of considerable generality. The scheme consists of applying the Cook-Weiss procedure to a cyclic -diketone, transforming the carbonyl groups of the product into a pair of olefinic sites (with or without attachment of the methyl substituent), preparation of the bracketed semibullvalene via nickel carbonyl promoted cyclization of the doubly allylic dibromide, and finally flash vacuum pyrolysis of the semibullvalene. Cyclic voltammetric studies performed on the title compounds have quantified not only the standard electron-donating capacity of the pendant alkyl groups, but also the consequences of nonbonded steric interactions associated with maintaining a bridged structure as the cyclooctatetraene ring flattens. Microscale preparation of the dianion of 5d permitted measurement of its1H NMR spectrum. Whereas 5b–d reacted with (–)-ertifo-bornyltriazolinedione, the methyl congeners 15 and 21 did not. Chromatographic separation of the urazole diastereomers derived from 5c and 5d proved possible. Whereas hydrolysis-oxidation of individual adducts provided access to optically active 5c, 5d was invariably already racemized upon isolation. Thus, the latter experiences very rapid conversion to its enantiomer. The activation parameters for racemization within 5c were determined, and it is argued that these reflect exclusively the energetic costs of bond shifting within its [8]annulene core. © 1990, American Chemical Society. All rights reserved.
引用
收藏
页码:228 / 239
页数:12
相关论文
共 118 条
[71]  
NACE HR, 1962, ORG REACTIONS, V12, P57
[72]  
Oth J. F. M., 1971, PURE APPL CHEM, V25, P573, DOI DOI 10.1351/PAC197125030573
[73]   CORRECTION [J].
PAQUETTE, LA .
TETRAHEDRON LETTERS, 1987, 28 (38) :4354-4354
[74]   BELTING OF THE CYCLOOCTATETRAENE RING ACROSS THE TRANS-ANNULAR 1-POSITION AND 5-POSITION [J].
PAQUETTE, LA ;
TROVA, MP .
TETRAHEDRON LETTERS, 1987, 28 (25) :2795-2798
[75]   BOND FIXATION IN ANNULENES .13. KINETIC-ANALYSIS OF DYNAMIC BEHAVIOR IN PERIPHERALLY CROWDED CYCLOOCTATETRAENES - PROBE OF THE METHYL PHENYL DICHOTOMY IN TETRASUBSTITUTED DERIVATIVES [J].
PAQUETTE, LA ;
HANZAWA, Y ;
HEFFERON, GJ ;
BLOUNT, JF .
JOURNAL OF ORGANIC CHEMISTRY, 1982, 47 (02) :265-272
[76]   DYNAMIC PROPERTIES OF CHIRAL CYCLOOCTATETRAENES - TOTAL INHIBITION OF THE RACEMIZATION PROCESS BY 1,4-ANNULATION [J].
PAQUETTE, LA ;
TROVA, MP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (24) :8197-8201
[77]   BOND FIXATION IN ANNULENES .15. A TITANIUM(0)-MEDIATED SYNTHESIS OF A CYCLOOCTATETRAENE - PROBE OF THE RELATIVE SIZE OF THE INTERSTITIAL PHENYL SUBSTITUENT IN 1,3-DIMETHYL-2-PHENYLCYCLOOCTATETRAENE BY MEANS OF RACEMIZATION KINETICS [J].
PAQUETTE, LA ;
GARDLIK, JM ;
MCCULLOUGH, KJ ;
HANZAWA, Y .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (26) :7644-7648
[78]   BOND FIXATION IN ANNULENES .3. STRUCTURAL CONSEQUENCES OF TETRAMETHYL AND PENTAMETHYL SUBSTITUTION OF CYCLOOCTATETRAENE RING [J].
PAQUETTE, LA ;
PHOTIS, JM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1976, 98 (16) :4936-4945
[79]   BOND FIXATION IN ANNULENES .16. SYNTHESIS OF THE 1,2-DIMETHYL-3-PHENYLCYCLOOCTATETRAENE REVERSIBLE 1,8-DIMETHYL-2-PHENYLCYCLOOCTATETRAENE BOND SHIFT ISOMER PAIR - PROBE OF THE RELATIVE SIZE OF A FLANKING PHENYL SUBSTITUENT BY MEANS OF RACEMIZATION KINETICS [J].
PAQUETTE, LA ;
GARDLIK, JM ;
MCCULLOUGH, KJ ;
SAMODRAL, R ;
DELUCCA, G ;
OUELLETTE, RJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (26) :7649-7655
[80]   SYNTHESIS AND X-RAY CRYSTAL-STRUCTURE ANALYSIS OF A VICINALLY DINITRO-SUBSTITUTED BISHOMOPENTAPRISMANE [J].
PAQUETTE, LA ;
FISCHER, JW ;
ENGEL, P .
JOURNAL OF ORGANIC CHEMISTRY, 1985, 50 (14) :2524-2527