Monomeric Cobalt Oxazoline Palladacycles (COP). Useful catalysts for catalytic asymmetric rearrangement of allylic trichloroacetimidates

Journal of Organic Chemistry

Volumn 69, Issue 23, 2004, Pages 8101-8104

  Kirsch, Stefan F ^a   Overman, Larry E ^a   Watson, Mary P ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSTS; MONOMERS; ORGANIC SOLVENTS; POLARIZATION; PURIFICATION; SINGLE CRYSTALS; SOLUBILITY; X RAY ANALYSIS;

COBALT OXAZOLINE PALLADACYCLES (COP); ENANTIOMERS; LIGANDS; POLARITY; X-RAY STRUCTURE;

COBALT COMPOUNDS;

1,2 DICHLOROETHANE; ACETIC ACID ETHYL ESTER; ACETONE; ACETONITRILE; ACETYLACETONATE; ACETYLACETONATE[[ETA 5 2 [2' (4' METHYLETHYL)OXAZOLINYL]CYCLOPENTADIENYL,1 C,3' N][ETA 4 TETRAPHENYLCYCLOBUTADIENE]COBALT]PALLADIUM; COBALT; CYCLOHEXANE; HEXAFLUOROACETYLACETONATE; HEXAFLUOROACETYLACETONATE[ETA 5 2 [2' (4' METHYLETHYL)OXAZOLINYL]CYCLOPENTADIENYL,1 C,3' N][ETA 4 TETRAPHENYLCYCLOBUTADIENE]COBALT]PALLADIUM; LIGAND; OXAZOLINE DERIVATIVE; TOLUENE; TRICHLOROACETIMIDIC ACID; UNCLASSIFIED DRUG;

ARTICLE; ASYMMETRIC CATALYSIS; CATALYST; CHEMICAL STRUCTURE; CRYSTAL STRUCTURE; ENANTIOMER; ENANTIOSELECTIVITY; REACTION ANALYSIS; SOLUBILITY; X RAY CRYSTALLOGRAPHY;

EID: 8644276255     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo0487092     Document Type: Article

References (37)

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31. 4- tetraphenylcyclobutadiene)-cobalt part structure.
32. 16
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34. A control experiment demonstrated that the palladium(II) catalyst is required: stirring a solution of allylic imidate 4 in THF in the absence of 2 produced no detectable amounts of allylic amide 5 after 24 h at 50°C.
35. COP complex 2 (5 mol %) catalyzed the rearrangement of 4 also in 1,2-dichloroethane or ethyl acetate, providing 5 in 93% yield and 91% ee after 29 h (1,2-dichloroethane) or 90% yield and 92% ee after 29 h (EtOAc). In 1,4-dioxane or tert-butyl methyl ether, formation of 5 under similar conditions with catalyst 2 was not observed. The use of DMSO led to catalyst decomposition.
36. Heating 2 in THF at 50°C for times longer than 10 h results in some decomposition of the catalyst; reactions employing 1 mol % of catalyst should not be performed in THF.
37. Higher amounts of water slow the reaction significantly.