54625-15-9Relevant academic research and scientific papers
Thermal Decomposition of Tricarbonyliron Lactone Complexes
Annis, Gary D.,Ley, Steven V.,Self, Christopher R.,Sivaramakrishnan, Ramamoorthy
, p. 299 (1980)
Tricarbonyliron lactones, on warming in tetrahydrofuran or benzene, afford products derived from decarbonylation, decarboxylation, and rearrangement pathways.
Synthesis and Characterization of Diorganocobalt Chlorides by Aliphatic Vinylic C–Cl Bond Activation
Niu, Qingfen,Zhang, Shumiao,Li, Xiaoyan,Sun, Hongjian,Fuhr, Olaf,Fenske, Dieter
, p. 866 - 869 (2016)
Three diorganocobalt chlorides [CoClMe(PMe3)2–{(C5H6)–CH=O}] (4), [CoClMe(PMe3)2–{(C6H8)–CH=O}] (5), and [CoClMe(PMe3)2–{(C6H7/s
Efficient Access to All-Carbon Quaternary and Tertiary α-Functionalized Homoallyl-type Aldehydes from Ketones
Pace, Vittorio,Castoldi, Laura,Mazzeo, Eugenia,Rui, Marta,Langer, Thierry,Holzer, Wolfgang
supporting information, p. 12677 - 12682 (2017/09/08)
β,γ-Unsaturated aldehydes with all-carbon quaternary or tertiary α-centers were rapidly assembled from ketones through a unique synthetic operation consisting of 1) C1 homologation, 2) Lewis acid mediated epoxide–aldehyde isomerization, and 3) electrophilic trapping. The synthetic equivalence of a vinyl oxirane and a β,γ-unsaturated aldehyde is the key concept of this previously undisclosed tactic. Mechanistic studies and labeling experiments suggest that an aldehyde enolate is a crucial intermediate. The homologating carbenoid formation plays a critical role in determining the chemoselectivity.
COMPOUNDS AND METHODS OF TREATING OCULAR DISORDERS
-
, (2016/06/14)
A method of treating an ocular disorder in a subject associated with increased all-trans-retinal in an ocular tissue includes administering to the subject a therapeutically effective amount of a primary amine compound of formula (I); and pharmaceutically acceptable salts thereof.
Expansion of first-in-class drug candidates that sequester toxic all-trans-retinal and prevent light-induced retinal degeneration
Zhang, Jianye,Dong, Zhiqian,Mundla, Sreenivasa Reddy,Hu, X. Eric,Seibel, William,Papoian, Ruben,Palczewski, Krzysztof,Golczak, Marcin
, p. 477 - 491 (2015/01/30)
All-trans-retinal, a retinoid metabolite naturally produced upon photoreceptor light activation, is cytotoxic when present at elevated levels in the retina. To lower its toxicity, two experimentally validated methods have been developed involving inhibition of the retinoid cycle and sequestration of excess of all-trans-retinal by drugs containing a primary amine group. We identified the first-in-class drug candidates that transiently sequester this metabolite or slow down its production by inhibiting regeneration of the visual chromophore, 11-cis-retinal. Two enzymes are critical for retinoid recycling in the eye. Lecithin:retinol acyltransferase (LRAT) is the enzyme that traps vitamin A (all-trans-retinol) from the circulation and photoreceptor cells to produce the esterified substrate for retinoid isomerase (RPE65), which converts all-trans-retinyl ester into 11-cis-retinol. Here we investigated retinylamine and its derivatives to assess their inhibitor/substrate specificities for RPE65 and LRAT, mechanisms of action, potency, retention in the eye, and protection against acute light-induced retinal degeneration in mice. We correlated levels of visual cycle inhibition with retinal protective effects and outlined chemical boundaries for LRAT substrates and RPE65 inhibitors to obtain critical insights into therapeutic properties needed for retinal preservation.
The cinchona primary amine-catalyzed asymmetric epoxidation and hydroperoxidation of α,β-unsaturated carbonyl compounds with hydrogen peroxide
Lifchits, Olga,Mahlau, Manuel,Reisinger, Corinna M.,Lee, Anna,Fares, Christophe,Polyak, Iakov,Gopakumar, Gopinadhanpillai,Thiel, Walter,List, Benjamin
supporting information, p. 6677 - 6693 (2013/06/05)
Using cinchona alkaloid-derived primary amines as catalysts and aqueous hydrogen peroxide as the oxidant, we have developed highly enantioselective Weitz-Scheffer-type epoxidation and hydroperoxidation reactions of α,β-unsaturated carbonyl compounds (up to 99.5:0.5 er). In this article, we present our full studies on this family of reactions, employing acyclic enones, 5-15-membered cyclic enones, and α-branched enals as substrates. In addition to an expanded scope, synthetic applications of the products are presented. We also report detailed mechanistic investigations of the catalytic intermediates, structure-activity relationships of the cinchona amine catalyst, and rationalization of the absolute stereoselectivity by NMR spectroscopic studies and DFT calculations.
Total synthesis of (+)-cyperolone
Klahn, Philipp,Duschek, Alexander,Liebert, Clemence,Kirsch, Stefan F.
supporting information; experimental part, p. 1250 - 1253 (2012/05/19)
The total synthesis of (+)-cyperolone, an eudesmane-derived sesquiterpenoid from Cyperus rotundus, is described. The de novo synthesis was accomplished via a 15 step sequence starting from (R)-(-)-carvone. The synthetic route features a platinum-catalyzed
Catalytic asymmetric epoxidation of α-branched enals
Lifchits, Olga,Reisinger, Corinna M.,List, Benjamin
supporting information; experimental part, p. 10227 - 10229 (2010/09/06)
An asymmetric catalytic epoxidation of α-branched, α,β-unsaturated aldehydes is presented. A highly synergistic combination of a primary cinchona-based amine and a chiral phosphoric acid was found to promote the reaction with excellent enantiocontrol for α-monosubstituted and α,β-disubstituted enals.
The hetero-Diels-Alder addition of sulfur dioxide to 1-fluorobuta-1,3-dienes: The sofa conformations preferred by 6-fluorosultines (6-fluoro-3,6-dihydro-1,2-oxathiin-2-oxides) enjoy enthalpic and conformational anomeric effects
Roversi, Elena,Scopelliti, Rosario,Solari, Euro,Estoppey, Raphael,Vogel, Pierre,Brana, Pedro,Menendez, Bibiana,Sordo, Jose A.
, p. 1336 - 1355 (2007/10/03)
The reactivity of (E)- and (Z)-1-fluorobuta-1,3-diene ((E)- and (Z)-11), 2-fluorobutadiene (12), (E)- and (Z)-1-(fluoromethylidene)-2-methylidenecyclohexane ((E)- and (Z)-13) toward SO2 has been explored and compared with that of (Z)- and (E)-1-(fluoromethylidene)-2-methylidene-3,4-dihydronaphthalene ((Z)-8 and (E)-8). In agreement with quantum calculations, 12 is unreactive toward SO2 (no cycloaddition, only polymerization), whereas (E)-1-fluoro-1,3-dienes react more rapidly than their (Z)-isomers to give the corresponding 6-fluorosultines following the endo (Alder rule) mode of hetero-Diels-Alder addition, No sulfolene has been observed following the cheletropic mode of addition with the fluorodienes, in contrast to other substituted dienes. In agreement with the calculations, cis-2-fluoro-3,4-oxathiabenzobicyclo[4.4.0]dec-1(6),9-diene-4-oxide (cis-9, the sultine obtained by SO2 addition to (Z)-8 under conditions of kinetic control) adopts a sofa conformation with the oxygen atom of the ring lying in the average plane of the four carbon atoms of its sultine moiety when it is in the crystalline state at - 100 °C. A similar sofa conformation was found for its trans-isomer, trans-9, obtained by isomerization of cis-9 or by hetero-Diels-Alder addition of SO2 to (E)-8. Experiments (equilibrium constant for hetero-Diels-Alder additions, bond lengths, and bond angles in crystalline fluorosultines cis-9 and trans-9) and high-level quantum calculations on cis- and trans-6-fluoro-3,6-dihydro-1,2-oxathiin-2-oxide (cis- and trans-20) confirm the existence of a stabilizing, enthalpic, anomeric (gem-disubstitution by sulfinyloxy and fluoro groups) effect, which is interpreted in terms of (lone pair) n(O1) → σ*(C-F) hyperconjugative interactions. This effect is strongest in the sofa conformers with a gauche arrangement of the σ(O1,S2) and σ(C6,F) bonds. The calculations suggest also that n(O1) → σ*(S2,O2′), π*(S=O), and n(S2) → σ*(O1,C6) interactions intervene and affect the relative stability of the conformers (sofa, boat, pseudochair) found for 6-fluorosultines cis-and trans-20.
Synthesis with organoboranes V. Hydroxymethylation and formylation of cycloalkenes via allylic organopotassium and organoboron compounds
Zaidlewicz, Marek
, p. 103 - 107 (2007/10/02)
Allylic hydroxymethylation of cyclohexene and cyclooctene was achieved by metallation with trimethylsilylmethylpotassium followed by the reaction with formaldehyde. 1-Methylcycloalkenes were transformed into 2-methylenecycloalkane-1-methanols by the reaction of formaldehyde with allylic diethylboranes derived from these olefins via metallation-transmetallation.Conjugated cycloalkenecarboxaldehydes were obtained by oxidation of the hydroxymethylation products.
