153259-54-2Relevant articles and documents
Aromaticity-Controlled Energy Storage Capacity of the Dihydroazulene-Vinylheptafulvene Photochromic System
Skov, Anders B.,Broman, S?ren Lindb?k,Gertsen, Anders S.,Elm, Jonas,Jevric, Martyn,Cacciarini, Martina,Kadziola, Anders,Mikkelsen, Kurt V.,Nielsen, Mogens Br?ndsted
, p. 14567 - 14575 (2016)
Photochemical conversion of molecules into high-energy isomers that, after a stimulus, return to the original isomer presents a closed-cycle of light-harvesting, energy storage, and release. One challenge is to achieve a sufficiently high energy storage capacity. Here, we present efforts to tune the dihydroazulene/vinylheptafulvene (DHA/VHF) couple through loss/gain of aromaticity. Two derivatives were prepared, one with aromatic stabilization of DHA and the second of VHF. The consequences for the switching properties were elucidated. For the first type, sigmatropic rearrangements of DHA occurred upon irradiation. Formation of a VHF complex could be induced by a Lewis acid, but addition of H2O resulted in immediate regeneration of DHA. For the second type, the VHF was too stable to convert into DHA. Calculations support the results and provide new targets. We predict that by removing one of the two CN groups at C-1 of the aromatic DHA, the heat storage capacity will be further increased, as will the life-time of the VHF. Calculations also reveal that a CN group at the fulvene ring retards the back-reaction, and we show synthetically that it can be introduced regioselectively.
Efficient enzymatic kinetic resolution of 4-hydroxytetralone and 3-hydroxyindanone
Joly,Nair, Mangalam S.
, p. 2283 - 2287 (2001)
Both enantiomers of 4-acetoxy- and 4-hydroxytetralone have been obtained with high enantiomeric purity by kinetic resolution using enzymes. 3-Hydroxyindanone was successfully resolved using enzymatic transesterification. The absolute configuration of the products were established by literature precedence.
Anodic Oxidation of Active Methylene Groups in the Presence of Excess Carboxylic Acid
Koketsu, Jugo,Kurita, Masasi,Tamano, Michiko,Fuijmura, Yoshikazu,Ando, Fumio
, p. 2767 - 2769 (1993)
The anodic oxidation of anthrone, (9,(10H)-anthracenone), 9,10-dihydroanthracene and 1-tetralone in acetonitrile was studied under the presence of excess carboxylic acids.The oxidation of anthrone with acetic acid gave anthraquinone, 10-acetoxyanthrone and 10-methyl-10-acetoxyanthrone.A similar reaction of anthrone with propionic acid yielded 10-propionyloxyanthrone.The electronic oxidation of 9,10-dihydroanthracene yielded anthraquinone, anthrone, and 9-acetoxyanthrone under the same conditions.Also, 1-tetralone reacted with acetic acid and propionic acid at the 4 position of the carbonyl group, giving 4-acetoxy- and 4-propionyloxy-1-tetralone, respectively.
Effective oxidation of benzylic and alkane C-H bonds catalyzed by sodium o-iodobenzenesulfonate with Oxone as a terminal oxidant under phase-transfer conditions
Cui, Li-Qian,Liu, Kai,Zhang, Chi
experimental part, p. 2258 - 2265 (2011/05/08)
Catalytic oxidation of benzylic C-H bonds could be efficiently realized using IBS as a catalyst which was generated in situ from the oxidation of sodium 2-iodobenzenesulfonate (1b) by Oxone in the presence of a phase-transfer catalyst, tetra-n-butylammonium hydrogen sulfate, in anhydrous acetonitrile at 60 °C. Various alkylbenzenes, including toluenes and ethylbenzenes, several oxygen-containing functionalities substituted alkylbenzenes, and a cyclic benzyl ether could be efficiently oxidized. And, the same reagent system of cat. 1b/Oxone/cat. n-Bu4NHSO4 could be applied to the effective oxidation of alkanes as well.
Asymmetrie synthesis of bicyclic diol derivatives through metal and enzyme catalysis: Application to the formal synthesis of sertraline
Krumlinde, Patrik,Bogar, Krisztian,Baeckvall, Jan-E.
experimental part, p. 4031 - 4036 (2010/08/05)
Enzyme- and ruthenium-catalyzed dynamic kinetic asymmetric transformation (DYKAT) of bicyclic diols to their diacetates was highly enantio- and diastereoselective to give the corresponding diacetates in high yield with high enantioselectivity (99.9% ee). The enantiomerically pure diols are accessible by simple hydrolysis (NaOH, MeOH), but an alternative enzyme-catalyzed ester cleavage was also used to give the trans-diol (R,R)1b in extremely high diastereomeric purity (trans/cis = 99.9:0.1, >99.9% ee). It was demonstrated that the diols can be selectively oxidized to the ketoalcohols in a ruthenium-catalyzed Oppenauer-type reaction. A formal enantioselective synthesis of sertraline from a simple racemic cis/trans diol 1b was demonstrated.
Clean and efficient benzylic C-H oxidation in water using a hypervalent iodine reagent: Activation of polymeric iodosobenzene with KBr in the presence of montmorillonite-K10
Dohi, Toshifumi,Takenaga, Naoko,Goto, Akihiro,Fujioka, Hiromichi,Kita, Yasuyuki
experimental part, p. 7365 - 7368 (2009/05/07)
(Chemical Equation Presented) We have found that unreactive and insoluble polymeric iodosobenzene [PhIO]n induced aqueous benzylic C-H oxidation to effectively give arylketones, in the presence of KBr and montmorillonite-K10 (M-K10) clay. Water-soluble and reactive species 1 having the unique I(III)-Br bond, in situ generated from [PhIO]n and KBr, was considered to be the key radical initiator during the reactions.
Benzylic oxidation catalyzed by dirhodium(II,III) caprolactamate
Catino, Arthur J.,Nichols, Jason M.,Choi, Hojae,Gottipamula, Sidhartha,Doyle, Michael P.
, p. 5167 - 5170 (2007/10/03)
(Chemical Equation Presented) Dirhodium caprolactamate [Rh 2(cap)4] is an effective catalyst for benzylic oxidation with tert-butyl hydroperoxide (TBHP) under mild conditions. Sodium bicarbonate is the optimal base additive for substrate conversion. Benzylic carbonyl compounds are readily obtained, and a formal synthesis of palmarumycin CP 2 using this methodology is described.
