Trifluoromethyl-Substituted Benzocyclobutenone and Benzocyclobutenedione: The Structure Anomaly of (Benzocyclobutenedione)tricarbonylchromium Complexes

2019 ◽  
Vol 38 (15) ◽  
pp. 3039-3052 ◽  
Author(s):  
Monika Böning née Pfennig ◽  
Krishna Gopal Dongol ◽  
Geanne Marize Romero Boston ◽  
Stefan Schmitz ◽  
Rudolf Wartchow ◽  
...  
1984 ◽  
Vol 39 (2) ◽  
pp. 207-212 ◽  
Author(s):  
Karl Dimroth ◽  
Rüdiger Thamm ◽  
Hans Kaletsch

New 6π-tricarbonylchromiumpyrnftne complexes 5c and 5d could be synthesized from 2,6-di-rbutyl- and 2,4,6-tri-f-butylpyridines (3c and 3d) with chromium hexacarbonyl. They are characterized by their 1H and 13C NMR Spectra and their CO-frequencies which are rather similar to those of 6π-tricarbonylchromium-2,4 ,6-triphenyl [1] or 2,4,6-trw-butyl- [2] λ3-phosphorins. When 5d is reacted with lithiumphenyl, the phenyl residue adds to C-4, giving probably compound 7, which by methanolysis and allyl rearrangement of the hydrogen atom from position 4 to position 2 affords tricarbonylchromium-2,6-di-f-butyl-4-phenyl-1,2-dihydropyridine (8) in 56% yield. The 6π-tricarbonylchromium complexes of 2,4,6-triphenyl- or 2,4,6-tn-t-butyl-λ3-phosphorins react with lithiumorganic compounds by addition only to the phosphorus atom whose reaction with methyliodide lead to tricarbonylchromium-λ5-phosphorin-ylid complexes [2], 5 d is a well crystallized compound, the X-ray analysis of the first 6π-tricarbonylchromium pyridine derivate could be performed [3] and compared with the results of the X-ray analysis of 6π-tricarbonylchromiumx 2,4,6-triphenyl-λ3-phosphorin [4]


2001 ◽  
Vol 123 (21) ◽  
pp. 4904-4918 ◽  
Author(s):  
Craig A. Merlic ◽  
Michael M. Miller ◽  
Bruce N. Hietbrink ◽  
K. N. Houk

1997 ◽  
Vol 62 (23) ◽  
pp. 8264-8267 ◽  
Author(s):  
Jin Wook Han ◽  
Seung Uk Son ◽  
Young Keun Chung

2002 ◽  
Vol 74 (1) ◽  
pp. 57-62 ◽  
Author(s):  
Holger Butenschön

Tricarbonylchromium complexes of benzocyclobutenone, benzocyclobutenedione, and 1,3-indandione are readily prepared by hydrolysis of the complexes of the corresponding acetals. Reduction of the benzocyclobutenone complex gives rise to an oxy-anion-driven ring opening to the corresponding ortho-quinodimethane intermediate, which can be trapped with dienophiles. Addition of 1-ethoxy-1-lithioethene allows a stereoselective ring expansion followed by an anionic ketol rearrangement with complete diastereoselectivity. Addition of 1-lithio-1-methoxyallene gives rise to a rare anionic 1-vinylcyclobutenol-cyclohexadienol rearrangement. Diaddition of alkenylmetal reagents at both keto groups in benzoyclobutenedione complexes causes dianionic oxy-Cope rearrangements to occur at ­78 °C, which are followed by diastereoselective intramolecular aldol additions. In some cases, a completely regioselective mono hydrolysis of di(enolates) was observed. Dianionic oxy-Cope rearrangements can also be realized with unstrained benzil derivatives giving 1,6-hexanediones and the corresponding aldol adducts. The 1,2,3-indantrione complex is obtained by oxidation of the 1,3-indandione complex with dimethyldioxirane in good yield and reacts with its central ketone group in hetero Diels­Alder cycloadditions.


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