210700-51-9Relevant articles and documents
Syntheses of 13C2-labelled 11Z-retinals
McLean, Neville J.,Gansmuller, Axel,Concistre, Maria,Brown, Lynda J.,Levitt, Malcom H.,Brown, Richard C.D.
, p. 8404 - 8410 (2011/11/12)
To enable solid-state NMR investigations of the rhodopsin chromophore and its photointermediates, a series of 11Z-retinal isotopomers have been synthesised containing pairs of adjacent 13C labels at C9/C10, C10/C11 or C11/C12, respectively. The C9 labelled carbon atom was introduced through the Heck reaction of a 13C-labelled Weinreb acrylamide derivative, and the label at the C12 position derived from a 13C-containing ethoxy Bestmann-Ohira reagent. The 13C labels at C10 and C11 were introduced through the reaction of β-ionone with labelled triethyl phosphonoacetate.
A pericyclic cascade to the stereocontrolled synthesis of 9-cis- retinoids
Iglesias, Beatriz,Torrado, Alicia,De Lera, Angel R.,Lopez, Susana
, p. 2696 - 2705 (2007/10/03)
A domino reaction that is pericyclic in nature is thought to be triggered upon treatment of alkenynol 10 with arylsulfenyl chlorides. The process comprises an ordered sequence of sigmatropic rearrangements: a reversible [2,3]-allyl sulfenate to allyl sulfoxide shift, followed by a [2,3]-propargyl sulfenate to allenyl sulfoxide rearrangement, and last a stereodifferentiating [1,5]-sigmatropic hydrogen migration leading to polyene 13. The occurrence of the C7 to C11 hydrogen migration has been demonstrated by labeling experiments. The double diastereoselection of the [1,5]- sigmatropic hydrogen shift to afford a single isomer of the final polyene 13 is thought to arise from a combination of the electronic effect of the sulfoxide at one terminus, and the steric effect imparted by the bulky trimethylcyclohexenyl substituent at the other terminus. The overall process thus constitutes a stereoselective synthesis of an E,Z,Z-triene fragment from an alkenynol and, in particular, a retinoid with the 7E,9Z,11Z,13E configuration on the conjugated polyenic side chain. Application of this method to the synthesis of retinoids, including labeled analogues, is straightforward.
Stereoselective isomerization of 10-arylsulfenate-11,12- dehydroretinoids to 9-cis-retinoids
De Lera, Angel R.,Castro, Alejandro,Torrado, Alicia,Lopez, Susana
, p. 4575 - 4578 (2007/10/03)
The C7-C12 triene fragment of 9-cis-retinoids 8 was stereoselectively generated by treatment of propargylic alcohol 3 with phenylsulfenyl chloride/triethylamine at -78 °C, followed by stereospecific reduction of the resulting vinylsulfoxide (t-BuLi, MeLi, MeOH, -78 °C). Thus, 9-cis- retinoic acid 2, the natural ligand of the retinoid X receptor (RXR) was straightforwardly synthesized from 8 in two steps.
