210700-51-9

Usage

Chemical Properties

Orange Oil

Upstream product

• 937-32-6 4-nitrobenzenesulfenyl chloride 
• 154307-85-4 (2E,7E)-9-(tert-Butyl-dimethyl-silanyloxy)-3,7-dimethyl-1-(2,6,6-trimethyl-cyclohex-1-enyl)-nona-2,7-dien-5-yn-4-ol 
• 7669-54-7 2-nitrobenzenesulfenyl chloride 
• 103633-89-2 3-(β-ionilidene)-1-propyne 
• 152893-54-4 (E)-tert-butyl((3-iodobut-2-en-1-yl)oxy)dimethylsilane 
• 25576-25-4 (3E,5E)-4-methyl-6-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3,5-hexadien-1-yne 
• 3917-39-3 (2E,4E)-3-methyl-5-(2,6,6-trimethyl-1-cyclohexenyl)-2,4-pentadien-1-ol 
• 17974-55-9 (2E,4E)-ethyl 3-methyl-5-(2,6,6-trimethylcyclohex-1-enyl)penta-2,4-dienoate 
• 37384-77-3 ethyl β-ionylidene acetate 
• 3917-41-7 (2E,4E)-3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadienal 
• 79-77-6 (E)-β-ionone 
• 884845-78-7 N-benzyl-N-methoxy-3-(2,6,6-trimethyl-cyclohex-1-enyl)-acrylamide 
• 18162-48-6 tert-butyldimethylsilyl chloride 

Downstream Products

• 29443-88-7 (2E,6E,8E)-3,7-dimethyl-9-(2,6,6-trimethyl-cyclohex-1-enyl)-nona-2,6,8-trien-4-yn-1-ol 
• 885050-34-0 [9,10-13C₂]-11Z-retinol 
• 68-26-8 vitamine A 
• 22737-96-8 11-cis-retinol 
• 68-26-8 RETINOL 

Relevant academic research and scientific papers

Syntheses of 13C2-labelled 11Z-retinals

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.

Accurate measurements of 13C-13C J-couplings in the rhodopsin chromophore by double-quantum solid-state NMR spectroscopy

A new double-quantum solid-state NMR pulse sequence is presented and used to measure one-bond 13C-13C J-couplings in a set of 13C2-labeled rhodopsin isotopomers. The measured J-couplings reveal a perturbation of the electronic structure at the terminus of the conjugated chain but show no evidence for protein-induced electronic perturbation near the C11-C12 isomerization site. This work establishes NMR methodology for measuring accurate 1JCC values in noncrystalline macromolecules and shows that the measured J-couplings may reveal local electronic perturbations of mechanistic significance. Copyright

A pericyclic cascade to the stereocontrolled synthesis of 9-cis- retinoids

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.

Efficient synthesis of 11-cis-retinoids

The light sensitivity and unstable nature of 11-cis-retinoids makes them ideal visual chromophores in nature. The synthesis of 11-cis-retinal analogues is of paramount importance in bioorganic studies of rhodopsin, the photoreceptor of the visual transduction pathway, but the instability of 11- cis-retinoids complicates their synthesis and there is no general synthetic route. Common strategies to the cis geometry have failed in the case of 11- cis-retinoids, and most often low yields and complex isomeric mixtures are obtained. Herein we report an efficient, general, and mild preparation of 11- cis-retinoids by semi-hydrogenation of 11-yne-retinoid precursors with Cu/Ag- activated zinc dust.

Stereoselective isomerization of 10-arylsulfenate-11,12- dehydroretinoids to 9-cis-retinoids

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.