5299-99-0Relevant academic research and scientific papers
Synthetic control of retinal photochemistry and photophysics in solution
Bassolino, Giovanni,Sovdat, Tina,Liebel, Matz,Schnedermann, Christoph,Odell, Barbara,Claridge, Timothy D.W.,Kukura, Philipp,Fletcher, Stephen P.
supporting information, p. 2650 - 2658 (2014/03/21)
Understanding how molecular structure and environment control energy flow in molecules is a requirement for the efficient design of tailor-made photochemistry. Here, we investigate the tunability of the photochemical and photophysical properties of the retinal-protonated Schiff base chromophore in solution. Replacing the n-butylamine Schiff base normally chosen to mimic the saturated linkage found in nature by aromatic amines results in the reproduction of the opsin shift and complete suppression of all isomerization channels. Modification of retinal by directed addition or removal of backbone substituents tunes the overall photoisomerization yield from 0 to 0.55 and the excited state lifetime from 0.4 to 7 ps and activates previously inaccessible reaction channels to form 7-cis and 13-cis products. We observed a clear correlation between the presence of polarizable backbone substituents and photochemical reactivity. Structural changes that increase reaction speed were found to decrease quantum yields, and vice versa, so that excited state lifetime and efficiency are inversely correlated in contrast to the trends observed when comparing retinal photochemistry in protein and solution environments. Our results suggest a simple model where backbone modifications and Schiff base substituents control barrier heights on the excited-state potential energy surface and therefore determine speed, product distribution, and overall yield of the photochemical process.
Azetidinone-retinoid hybrids: Synthesis and differentiative effects
Pori, Matteo,Galletti, Paola,Soldati, Roberto,Calzà, Laura,Mangano, Chiara,Giacomini, Daria
, p. 857 - 863 (2013/12/04)
As a part of a systematic investigation on the synthesis and biological activities of new β-lactam compounds, we examined β-lactam candidates 1, 2E and 2Z and their ability to induce cell proliferation or differentiation. Azetidinone 1 was chosen for its
Base-induced decarboxylation of polyunsaturated α-cyano acids derived from malonic acid: Synthesis of sesquiterpene nitriles and aldehydes with β-, φ-, and ψ-end groups
Dufossé, Laurent,Cartier, Dominique,Valla, Benoist,Fouillaud, Mireille,Labia, Roger,Valla, Alain
, p. 259 - 265 (2013/03/28)
Catalytic base-induced decarboxylation of polyunsaturated α-cyano-β-methyl acids derived from malonic acid led to the corresponding nitriles 3 (Schemes 2 and 3), 6 (Scheme 5), and 9 (Scheme 6). This decarboxylation occurred with previous deconjugation of
New syntheses of retinal and its acyclic analog γ-retinal by an extended aldol reaction with a C6 building block that incorporates a C5 unit after decarboxylation. A formal route to lycopene and β-carotene
Valla, Alain,Valla, Benoist,Le Guillou, Regis,Cartier, Dominique,Dufosse, Laurent,Labia, Roger
, p. 512 - 520 (2008/02/07)
Since the C15 β-end-group aldehyde 10 ((β-ionylidene) acetaldehyde), an excellent intermediate in the syntheses of retinoids, can be synthesized in many ways from β-ionone, and since the corresponding acyclic C15 ψ-end-group aldehyde 5 can easily be synthesized from citral (1) (Scheme 3), we applied the C15 + C5 route to the syntheses of γ-retinal ((all-E)-8) (Scheme 3) and retinal ((all-E)-13) (Scheme 4), and therefore, by coupling (2 x C20 → C 40), to the preparation of lycopene (14) and β-carotene (15) (Scheme 5). Our new syntheses of retinal ((all-E)-13) and γ-retinal ((all-E)-8 use an extended aldol reaction with a C6 building block that incorporates a C5 unit after decarboxylation.
Simple and efficient preparation of [10,20-13C2]- and [10-CH3,13-13C2]-10-methylretinal: Introduction of substituents at the 2-position of 2,3-unsaturated nitriles
Verdegem,Monnee,Lugtenburg
, p. 1269 - 1282 (2007/10/03)
In this paper, we present the synthesis of [10,20-13C2]-10-methylretinal and [10-CH3,13-13C2]-10-methylretinal, two doubly 13C-labeled chemically modified retinals that have been recently used to study the structural and functional details behind the photocascade of bovine rhodopsin (Verdegem et al. Biochemistry 1999, 38, 11316; de Lange et al. Biochemistry 1998, 37, 1411). To obtain both doubly 13C-labeled compounds, we developed a novel synthetic method to directly and regiospecifically introduce a methyl substituent on the 2-position of 3-methyl-5-(2′,6′,6′-trimethyl-1′ -cyclohexen-1′-yl)-2,4-pentadienenitrile. Encouraged by these results, we investigated the scope of this novel reaction by developing a general method for the introduction of a variety of substituents to the 2-position of 3-methyl-2,3-unsaturated nitriles, paving the way for simple and efficient synthesis of a wide variety of 10-, 14-, and 10,14-substituted chemically modified retinals, and other biologically important compounds.
New preparation of an important synthon for vitamin A synthesis
Andriamialisoa, Zo,Valla, Alain,Zennache, Sakina,Giraud, Michel,Potier, Pierre
, p. 8091 - 8092 (2007/10/02)
The "C-18 ketone" 1, key intermediate for vitamin A synthesis, is prepared in a few steps from β-ionone 3 via β-ionylidene acetonitrile 2 (32% overall yield).
Polymer-supported Phosphonates. Olefins from Aldehydes, Ketones, and Dioxolans by means of Polymer-supported Phosphonates
Cainelli, Gianfranco,Contento, Michele,Manescalchi, Francesco,Regnoli, Rodolfo
, p. 2516 - 2519 (2007/10/02)
Phosphonates substituted with electron-withrdrawing groups (CN and CO2Me) have been supported, by means of a neutralization reaction, on the macroreticular anion-exchange resin Amberlyst A-26.Treatment of carbonyl compounds with the polymer-bound phosphonate in various solvents gave olefins in high yields, at room temperature.Either batch or column techniques are employed, the latter offering the opportunity of a continuous procedure.The simultaneous use of the phosphonate resin and of an acidic one (Amberlyst 15 H) allowed the direct sequential hydrolysis and olefination of dioxolans.
