Electronic structure of certain carbonyl compounds containing a conjugated dimethylamino group

1976 ◽  
Vol 10 (4) ◽  
pp. 448-452
Author(s):  
V. G. Tishchenko ◽  
M. M. Fetisova
Keyword(s):  
Electronic Structure ◽  
Carbonyl Compounds ◽  
Dimethylamino Group

Reactions of phenyldimethylsilyllithium with β-N,N-dimethylaminoenones: A convenient synthesis of β-dimethyl(phenyl)silylacrylic acid and its derivatives

2004 ◽  
Vol 82 (2) ◽  
pp. 325-332 ◽  
Author(s):  
Ian Fleming ◽  
Elena Marangon ◽  
Chiara Roni ◽  
Matthew G Russell ◽  
Sandra Taliansky Chamudis
Keyword(s):  
Key Words ◽  
Methyl Iodide ◽  
Carbonyl Compounds ◽  
Conjugate Addition ◽  
Brief Treatment ◽  
Dimethylamino Group ◽  
Convenient Synthesis ◽  
Work Up

Phenyldimethylsilyllithium reacted with 5,5-dimethyl-3-(N,N-dimethylamino)cyclohex-2-enone (7), 3-(E)-N,N-dimethylaminopropenal (11), and 4-N,N-dimethylaminobut-3-en-2-one (13) to give the corresponding β-silyl-α,β-unsaturated carbonyl compounds 8, 12, and 14, in which the dimethylamino group has been displaced by the phenyldimethylsilyl group. Phenyldimethylsilyllithium reacted with ethyl β-N,N-dimethylaminopropenoate (15) by conjugate addition, but, in contrast to the ketones 7 and 13 and the aldehyde 11, the intermediate enolate 16 was C-protonated in the aqueous work-up to give ethyl 3-N,N-dimethylamino-3-dimethyl(phenyl)silylpropanoate (17). When the enolate 16 was instead given a mysteriously brief treatment with methyl iodide before work-up, the product was ethyl 3-(E)-dimethy(phenyl)silylpropenoate (18). Phenyllithium and methyllithium also added conjugatively to ethyl β-N,N-dimethylaminoacrylate (15) but, in contrast to the silyl case, the intermediate enolate 22 reacted unexceptionally with methyl iodide to give the products 25 and 26 of stereoselective C-methylation. This synthesis of the ester 18 was used to synthesize the Oppolzer sultam derivative 30.Key words: conjugate addition, elimination, substitution, silyllithium, silylenone.

The electronic structure of polyenes and unsaturated carbonyl compounds

Tetrahedron ◽  
1978 ◽  
Vol 34 (24) ◽  
pp. 3591-3598 ◽  
Author(s):  
Martin Klessinger ◽  
Ekkehard Gunkel
Keyword(s):  
Electronic Structure ◽  
Carbonyl Compounds

Carbonyl compounds of Rh, Ir, and Mt: electronic structure, bonding and volatility

2020 ◽  
Vol 22 (33) ◽  
pp. 18681-18694
Author(s):  
M. Iliaš ◽  
V. Pershina
Keyword(s):  
Electronic Structure ◽  
Carbonyl Compounds ◽  
Relativistic Effects ◽  
Bond Dissociation Energies ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Relativistic Dft

First bond dissociation energies and other properties have been predicted for carbonyl compounds of group-9 elements including those of element 109, Mt, from relativistic DFT and CC calculations. A remarkable Λ-shape of the trends is observed, caused by strong relativistic effects on the valence AOs of Mt.

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