18486-69-6Relevant articles and documents
Hydroxylation by Cytochrome P-450 and Metalloporphyrin Models. Evidence for Allylic Rearrangement
Groves, John T.,Subramanian, Durga V.
, p. 2177 - 2181 (1984)
The allylic hydroxylation of 3,3,6,6-tetradeuteriocyclohexene, methylenecyclohexane, and β-pinene has been examined with phenobarbital-induced liver microsomal cytochrome P-450 (P-450LM2) and with iron porphyrin and chromium porphyrin model systems.Aerobic and peroxide dependent enzymic regimes were investigated with purified P-450LM2 and with microsomal suspensions.Epoxidation and allylic hydroxylation were primary reactions with all substrates.With 3,3,6,6-tetradeuteriocyclohexene, the major hydroxylation product (60-80percent) was the result of hydroxylation at the deuterated allylic site.In all cases, a significant amount (20-40percent) of hydroxylation occurred with allylic rearrangement.The iron porphyrin/iodosylbenzene model system also showed preferential hydroxylation of the deuterated allylic site (70percent) with significant allylic rearrangement (30percent).By contrast, the chromium porphyrin/iodosylbenzene model system showed complete scrambling of the allylic system.Extensive rearrangement accompanied the hydroxylation of methylenecyclohexane and β-pinene by both the enzymic and metalloporphyrin systems whereas the selenium dioxide oxidation of these substrates gave selective allylic hydroxylation without rearrangement.A mechanism is suggested for allylic hydroxylation by cytochrome P-450 and by the metalloporhyrin model systems involving initial hydrogen atom abstraction from the allylic site and geminate, cage recombination of the incipient, allylic free radical.
Synthesis of Chiral Hydroxythiols Based on Oxygen-Containing α- And β-Pinene Derivatives
Banina,Sudarikov,Krymskaya,Frolova,Kuchin
, p. 261 - 265 (2015)
Isomeric 10-thiopinan-3-ols including (1S,2S,3S,5R)-6,6-dimethyl-2-(sulfanylmethyl)bicyclo[3.1.1]heptan-3-ol were synthesized for the first time from oxygen-containing α- and β-pinene derivatives.
Monoterpene-containing substituted coumarins as inhibitors of respiratory syncytial virus (Rsv) replication
Borisevich, Sophia S.,Galochkina, Anastasia V.,Khomenko, Tatyana M.,Korchagina, Dina V.,Nikolaeva, Yulia V.,Petukhova, Galina D.,Salakhutdinov, Nariman F.,Shtro, Anna A.,Volcho, Konstantin P.
, (2021/12/24)
Respiratory syncytial virus (RSV) is a critical cause of infant mortality. However, there are no vaccines and adequate drugs for its treatment. We showed, for the first time, that O-linked coumarin–monoterpene conjugates are effective RSV inhibitors. The most potent compounds are active against both RSV serotypes, A and B. According to the results of the time-of-addition experiment, the conjugates act at the early stages of virus cycle. Based on molecular modelling data, RSV F protein may be considered as a possible target.
Asymmetric Synthesis of Oxygenated Monoterpenoids of Importance for Bark Beetle Ecology
Ganji, Suresh,Svensson, Fredric G.,Unelius, C. Rikard
, p. 3332 - 3337 (2020/11/30)
Herein we report the asymmetric syntheses of a number of oxygenated terpenoids that are of importance in the chemical ecology of bark beetles. These are pinocamphones, isopinocamphones, pinocarvones, and 4-thujanols (= sabinene hydrates). The camphones were synthesized from isopinocampheol, the pinocarvones from β-pinene, and the thujanols from sabinene. The NMR spectroscopic data, specific rotations, and elution orders of their stereoisomers on a chiral GC-phase (β-cyclodextrin) are also reported. This enables facile synthesis of pure compounds for biological activity studies and identification of stereoisomers in mixed natural samples.
A Simple, Mild and General Oxidation of Alcohols to Aldehydes or Ketones by SO2F2/K2CO3 Using DMSO as Solvent and Oxidant
Zha, Gao-Feng,Fang, Wan-Yin,Leng, Jing,Qin, Hua-Li
supporting information, p. 2262 - 2267 (2019/04/17)
A practical, general and mild oxidation of primary and secondary alcohols to carbonyl compounds proceeds in yields of up to 99% using SO2F2 as electrophile in DMSO as both the oxidant and the solvent at ambient temperature. No moisture- and oxygen-free conditions are required. Stoichiometric amount of inexpensive K2CO3, which generates easy to separate by-products, is used as the base. Thus, 5-gram scale runs proceeded in nearly quantitative yields by a simple filtration as the work-up. The use of a polar solvent such as DMSO, which usually promotes competing Pummerer rearrangement, is also noteworthy. This protocol is compatible with a variety of common N-, O-, and S-functional groups on (hetero)arene, alkene and alkyne substrates (68 examples). The protocol was applied (99% yield) to a formal synthesis of the important cholesterol-lowering drug Rosuvastatin. (Figure presented.).
Oxidation of secondary alcohols using solid-supported hypervalent iodine catalysts
Ballaschk, Frederic,Kirsch, Stefan F.
supporting information, p. 5896 - 5903 (2019/11/11)
It is shown how secondary alcohols are oxidized to provide the corresponding ketones by use of Oxone and solid-supported hypervalent iodine catalysts. Under experimentally simple conditions with acetonitrile at elevated temperatures, excellent conversions were achieved with low catalyst loadings (0.2-5 mol%) when employing the conjugates 5 and 6 derived from IBX and IBS. The catalysts are broadly applicable to a range of alcohol substrates. Of primary importance with respect to sustainability issues, the metal-free catalysts are easily removed from the reaction mixture through filtration, and they can be re-used in oxidation processes for multiple times, without loss of catalytic activity.
IBX as a catalyst for dehydration of hydroperoxides: Green entry to α,β-unsaturated ketones: Via oxygenative allylic transposition
Kuga, Tetsuya,Sasano, Yusuke,Iwabuchi, Yoshiharu
supporting information, p. 798 - 801 (2018/02/06)
A catalytic transformation of allylic hydroperoxides into α,β-unsaturated carbonyl compounds using IBX as a dehydration catalyst is described. The combination of a singlet oxygen ene reaction and the IBX-catalyzed dehydration provides α,β-unsaturated carbonyl compounds from alkenes via oxygenative allylic transposition with H2O as the only byproduct.
The Taiji and Eight Trigrams chemistry philosophy of chiral iridium(III) complexes with triplex stereogenic centers
Yan, Zhi-Ping,Luo, Xu-Feng,Liao, Kang,Lin, Zi-Xuan,Wu, Zheng-Guang,Zhou, Yong-Hui,Zheng, You-Xuan
supporting information, p. 4045 - 4048 (2018/03/26)
Four novel chiral iridium(iii) complexes with triplex stereogenic centers were synthesized by introducing chiral carbon atoms into cyclometalated and ancillary ligands, and separated into eight isomers, which coincide with the old Chinese philosophy Eight Trigrams. The electron circular dichroism and circularly polarized luminescence spectra of four pairs of isomers show perfect mirror images with a dissymmetry factor (glum factor) of around 0.003.
Selectivity Modulation of the Ley–Griffith TPAP Oxidation with N-Oxide Salts
Moore, Peter W.,Jiao, Yanxiao,Mirzayans, Paul M.,Sheng, Lexter Ng Qi,Hooker, Jordan P.,Williams, Craig M.
, p. 3401 - 3407 (2016/07/26)
A wide variety of novel non-hygroscopic N-oxide tetraphenylborate salts were synthesized and evaluated as co-oxidants in the Ley–Griffith (TPAP) oxidation of benzylic and allylic alcohols under non-anhydrous conditions. The novel DABCOO·TPB (2:1) salt was herein unearthed as a viable competitor to the first-generation NMO·TPB (2:1) salt, but more importantly gave increased performance under oxidative competition. X-ray crystal structure analysis and NMR spectroscopy revealed that depending on the crystallization conditions 1:1, 2:1 or 3:2 N-oxide–tetraphenylborate salts could be formed.
Oxidation of alcohols by TBHP in the presence of sub-stoichiometric amounts of MnO2
Bhaumik, Chanchal,Stein, Dominique,Vincendeau, Sandrine,Poli, Rinaldo,Manoury, éric
, p. 566 - 570 (2016/06/01)
Commercially available activated MnO2 has been investigated as a catalyst for the oxidation of alcohols (phenylethanol, 4-methyl- and 4-methoxybenzyl alcohol, trans-cinnamyl alcohol, cyclohexanol, menthol, perillyl alcohol and myrtenol) by TBHP/decane or TBHP/water in MeCN. The activity is highest for benzylic and allylic alcohols. Secondary alcohols yield ketones with good selectivities, while the aldehydes generated from primary alcohols are further oxidized. The process competes with the TBHP catalyzed decomposition. It thus requires the use of excess TBHP and high catalyst loadings to achieve high conversions. However, the low cost of the reagents makes this new protocol convenient for the oxidation of reactive secondary alcohols. The study also suggests that MnO2 should be proscribed as a reagent to quench excess TBHP in oxidative processes when the synthetic target contains easily oxidizable alcohol functions and when carrying our detailed kinetic monitoring of oxidation processes.
