1ST DIRECT NMR SPECTROSCOPIC OBSERVATION OF A CRAM-CHELATE INVOLVING A CHIRAL ALPHA-ALKOXY ALDEHYDE

被引：18

作者：

REETZ, MT ^{[1
]}

RAGUSE, B ^{[1
]}

SEITZ, T ^{[1
]}

机构：

[1] UNIV MARBURG,FACHBEREICH CHEM,D-35043 MARBURG,GERMANY

来源：

TETRAHEDRON | 1993年 / 49卷 / 38期

关键词：

D O I：

10.1016/S0040-4020(01)96262-3

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The reaction of CH3TiCl3 with 2-benzyloxy propanal 10 at low temperatures in CD2Cl2 leads to the formation of two diastereomeric Cram-type chelates 13a/13b which can be observed directly by C-13-NMR spectroscopy. The octahedral chelates undergo C-C bond formation with rust order kinetics, suggesting intramolecular 1,3 methyl transfer. Crossover experiments are unsuitable for definitive proof of intramolecularity due to ligand exchange reactions prior to Grignard-type addition.

引用

收藏

页码：8561 / 8568

页数：8

相关论文

共 21 条

[1] CHELATES AS INTERMEDIATES IN NUCLEOPHILIC ADDITIONS TO ALKOXY KETONES ACCORDING TO CRAM RULE (CYCLIC MODEL) [J].

CHEN, XN ;

HORTELANO, ER ;

ELIEL, EL ;

FRYE, SV .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (05) :1778-1784

[2] CHEMISTRY OF METHYLTITANIUM TRICHLORIDE - SYNTHESIS, PROPERTIES, INFRARED SPECTRA, AND VARIABLE TEMPERATURE NUCLEAR MAGNETIC RESONANCE SPECTRA OF ADDUCTS OF METHYLTITANIUM TRICHLORIDE WITH SYMMETRICAL BIDENTATE LIGANDS [J].

CLARK, RJH ;

MCALEES, AJ .

JOURNAL OF THE CHEMICAL SOCIETY A -INORGANIC PHYSICAL THEORETICAL, 1970, (12) :2026-&

[3] CHEMISTRY OF METHYLTITANIUM TRICHLORIDE .2. VARIABLE-TEMPERATURE NUCLEAR MAGNETIC-RESONANCE AND INFRARED-SPECTRA OF SOME COMPLEXES OF METHYLTITANIUM TRICHLORIDE AND OF TITANIUM TETRACHLORIDE WITH UNSYMMETRICAL BIDENTATE LIGANDS [J].

CLARK, RJH ;

MCALEES, AJ .

INORGANIC CHEMISTRY, 1972, 11 (02) :342-&

[4] STUDIES IN STEREOCHEMISTRY .30. MODELS FOR STERIC CONTROL OF ASYMMETRIC INDUCTION [J].

CRAM, DJ ;

KOPECKY, KR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1959, 81 (11) :2748-2755

[5] EVIDENCE FOR CARBON HYDROGEN TITANIUM INTERACTIONS - SYNTHESIS AND CRYSTAL-STRUCTURES OF THE AGOSTIC ALKYLS [TICL3(ME2PCH2CH2PME2)R] (R=ET OR ME) [J].

DAWOODI, Z ;

GREEN, MLH ;

MTETWA, VSB ;

PROUT, K ;

SCHULTZ, AJ ;

WILLIAMS, JM ;

KOETZLE, TF .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1986, (08) :1629-1637

[6]

ELIEL EL, 1983, ASYMMETRIC SYNTHESIS, V2, P125

[7] ACYCLIC STEREOSELECTION .12. DOUBLE STEREODIFFERENTIATION WITH MUTUAL KINETIC RESOLUTION - A SUPERIOR CLASS OF REAGENTS FOR CONTROL OF CRAMS RULE STEREOSELECTION IN SYNTHESIS OF ERYTHRO-ALPHA-ALKYL-BETA-HYDROXY CARBOXYLIC-ACIDS FROM CHIRAL ALDEHYDES [J].

HEATHCOCK, CH ;

PIRRUNG, MC ;

LAMPE, J ;

BUSE, CT ;

YOUNG, SD .

JOURNAL OF ORGANIC CHEMISTRY, 1981, 46 (11) :2290-2300

[8] THEORETICAL-STUDIES OF ORGANOMETALLIC COMPOUNDS .2. ALL ELECTRON AND PSEUDOPOTENTIAL CALCULATIONS OF M(CH3)NCL4-N (M = C, SI, GE, SN, PB N = 0-4) [J].

JONAS, V ;

FRENKING, G ;

REETZ, MT .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 1992, 13 (08) :935-943

[9] STRONGLY PREFERENTIAL ALKYLATION AND CARBONYL OLEFINATION OF ALPHA-HYDROXYCARBONYL AND BETA-HYDROXYCARBONYL COMPOUNDS BY ORGANO-TRANSITION METAL REAGENTS IN COMPETITION EXPERIMENTS WITH THE CORRESPONDING DEOXY COMPOUNDS [J].

KAUFFMANN, T ;

MOLLER, T ;

RENNEFELD, H ;

WELKE, S ;

WIESCHOLLEK, R .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1985, 24 (04) :348-350

[10] ALPHA-ELIMINATION VERSUS BETA-ELIMINATION IN THE CLEAVAGE OF ETHERS BY ORGANOALKALI METAL COMPOUNDS [J].

LETSINGER, RL ;

POLLART, DF .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1956, 78 (23) :6079-6085