LITHIO-DIAZOMETHANE AND LITHIO-(TRIMETHYLSILYL)DIAZOMETHANE - THEORETICAL AND EXPERIMENTAL STUDIES OF THEIR STRUCTURES, REACTIONS AND REACTION-PRODUCTS

被引:26
作者
BOCHE, G
LOHRENZ, JCW
SCHUBERT, F
机构
[1] Fachbereich Chemie der Philipps-Universität Marburg
关键词
D O I
10.1016/S0040-4020(01)90444-2
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The first report of a metalated diazomethane by Eugen Muller and his coworkers appeared in 1933. Then, in a thirty-six years ongoing story, 1-6 this group revealed highly interesting but also puzzling details about the chemistry of metalated diazomethane and metalated substituted diazomethanes: 1. Metalation of diazomethane 1a (the parent compound) to give the corresponding Li (or Na) species followed by protonation led to ''isodiazomethane'' which finally turned out to be N-isocyano amine 1c. Ab initio calculations of the structures and energies of the three non-cyclic CH2N2 isomers 1a-c and of the four non-cyclic lithiated diazomethane isomers 2-Li(I)-2-Li(IV), as well as their dimers, provide an understanding of this reaction sequence. 2. Metalation of mono-substituted diazomethanes RCHN(2), R = Ph, Me, Me(3)Si, e.g. by methyllithium, followed by protonation, resulted in a completely different observation, namely the formation of 4,5-bis-R-substituted 1,2,3-triazoles (e.g. 10) and methylamine 11. In the crystals of lithiated trimethylsilyl-diazomethane 13-Li, which allowed for the first time to determine the crystal structure of a lithiated (substituted) diazomethane, is also present the corresponding Li-triazole 14-Li ([6 13-Li . 2 14-Li . 6 Et(2)O . hexane]). Model calculations traced the pathway of the triazole formation via a nitrenoid (e.g. 9.Li) which is also responsible for the formation of methylamine 11. The completely different chemistry of diazomethane 1a and mono-substituted diazomethanes in the deprotonation-protonation sequence is due to the different structures of the corresponding Li(Na) species and their different reactivities (selectivities).
引用
收藏
页码:5889 / 5902
页数:14
相关论文
共 40 条
[1]  
[Anonymous], 1986, AB INITIO MOL ORBITA
[2]  
AOYAMA T, 1982, CHEM PHARM BULL, V30, P3450
[3]   NEW METHODS AND REAGENTS IN ORGANIC-SYNTHESIS .52. LITHIUM TRIMETHYLSILYLDIAZOMETHANE - A NEW SYNTHON FOR THE PREPARATION OF 1-SUBSTITUTED 5-HYDROXY-1,2,3-TRIAZOLES FROM ISOCYANATES [J].
AOYAMA, T ;
KABEYA, M ;
FUKUSHIMA, A ;
SHIOIRI, T .
HETEROCYCLES, 1985, 23 (09) :2363-2366
[4]   NEW METHODS AND REAGENTS IN ORGANIC-SYNTHESIS .53. LITHIUM TRIMETHYLSILYLDIAZOMETHANE - A NEW SYNTHON FOR THE PREPARATION OF 2-AMINO-1,3,4-THIADIAZOLES FROM ISOTHIOCYANATES [J].
AOYAMA, T ;
KABEYA, M ;
FUKUSHIMA, A ;
SHIOIRI, T .
HETEROCYCLES, 1985, 23 (09) :2367-2369
[5]   NEW METHODS AND REAGENTS IN ORGANIC-SYNTHESIS .54. LITHIUM TRIMETHYLSILYLDIAZOMETHANE - A NEW SYNTHON FOR THE PREPARATION OF 1-SUBSTITUTED 5-ALKYLTHIO-1,2,3-TRIAZOLES FROM ISOTHIOCYANATES [J].
AOYAMA, T ;
KABEYA, M ;
SHIOIRI, T .
HETEROCYCLES, 1985, 23 (09) :2371-2374
[6]  
AOYAMA T, 1982, CHEM PHARM BULL, V30, P3849
[7]   DIAZOMETHANES .29. REACTIONS WITH TAUTOMERIC DIAZOMETHYL ANION [J].
BEUTLER, R ;
ZEEH, B ;
MULLER, E .
CHEMISCHE BERICHTE-RECUEIL, 1969, 102 (08) :2636-&
[8]   [TERT-BUTYLCYANIDE.LITHIUM BIS(TRIMETHYLSILYL)-AMIDE]2, A MODEL OF THE INTERMEDIATE RCN.MR' COMPLEX FORMED IN REACTIONS OF CYANIDES RCN WITH ORGANOMETALLIC COMPOUNDS R'M [J].
BOCHE, G ;
LANGLOTZ, I ;
MARSCH, M ;
HARMS, K ;
FRENKING, G .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1993, 32 (08) :1171-1173
[9]  
BOCHE G, 1994, ANGEW CHEM, V106, P90
[10]  
Boche G., 1993, ANGEW CHEM, V105, P1207