24336-19-4Relevant 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.
, 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.
The Suzuki Reaction in Stereocontrolled Polyene Synthesis: Retinol (Vitamin A), its 9- and/or 13-Demethyl Analogs, and Related 9-Demethyl-dihydroretinoids
Torrado, Alicia,Iglesias, Beatriz,Lopez, Susana,Lera, Angel R. de
, p. 2435 - 2454 (2007/10/02)
A new synthesis of retinol (vitamin A) and 9- and/or 13-demethylretinols, with essentially complete control of regio- and stereochemistry, is described which is based on the thallium-accelerated, palladium-catalyzed cross-coupling reactions of (E)-1-alkenylboronic acids and (E)-1-alkenyl iodides (Suzuki reaction).The procedure has also been extended to the stereocontrolled synthesis of a series of 9-demethyl-dihydroretinoids of potential biological interest.
Stereospecific Synthesis of 9-Demethylretinoids via Palladium-Catalyzed Vinylboronic Acid-Vinyl Iodide Cross Coupling
Lera, Angel R. de,Torrado, Alicia,Iglesias, Beatriz,Lopez, Susana
, p. 6205 - 6208 (2007/10/02)
A stereospecific synthesis of 9-demethylretinoids with either trans or 11-cis geometries, based on the thallium-accelerated palladium-catalyzed cross-coupling reactions of (E)-1-alkenylboronic acid and (E) or (Z)-alkenyl iodides, is described.
Synthesis of specifically deuteriated 9- and 13-demethylretinals
Berg, Ellen M. M. van den,Bent, Arie van der,Lugtenburg, Johan
, p. 160 - 167 (2007/10/02)
(13-2H)13-Demethylretinal, (11,12,13-2H3)13-demethylretinal, (9-2H)9-demethylretinal and (9,10-2H2)9-demethylretinal were prepared in all-E, 9Z, 11Z and 13Z isomeric form with high deuterium incorporation.In the
Preparation of 11,14-epoxy-bridged and isomeric chain-demethylated retinals. 13-Demethyl-11,14-epoxy-, 9-demethyl-, 13-demethyl- and 9,13-bisdemethyl-retinals
Broek, A. D.,Muradin-Szweykowska, M.,Courtin, J. M. L.,Lugtenburg, J.
, p. 46 - 51 (2007/10/02)
9-Cis- and all-trans-13-demethyl-11,14-epoxyretinyl acetate were prepared via a Wittig coupling between β-ionylidenetriphenylphosphonium bromide (1) and 5-(acetoxymethyl)furfural.Saponification of these acetates, subsequent oxidation and HPLC separation a
