4370-02-9Relevant articles and documents
Homochiral (1S,2R)-1,2-indandiol from asymmetric reduction of 1,2-indanedione by resting cells of the yeast Trichosporon cutaneum
Conceicao, Gelson J. Andrade,Moran, Paulo J. S.,Rodrigues, J. Augusto R.
, p. 2327 - 2330 (2003)
A concise highly diastereo- and enantioselective preparation of homochiral (1S,2R)-1,2-indandiol 1 (75% yield, >99% e.e.) by asymmetric reduction of 1,2-indanedione 5 mediated by fresh resting cells of Trichosporon cutaneum CCT 1903 is reported.
A Ruthenium(II)-Copper(II) Dyad for the Photocatalytic Oxygenation of Organic Substrates Mediated by Dioxygen Activation
Iali, Wissam,Lanoe, Pierre-Henri,Torelli, Stéphane,Jouvenot, Damien,Loiseau, Frédérique,Lebrun, Colette,Hamelin, Olivier,Ménage, Stéphane
, p. 8415 - 8419 (2015)
Dioxygen activation by copper complexes is a valuable method to achieve oxidation reactions for sustainable chemistry. The development of a catalytic system requires regeneration of the CuI active redox state from CuII. This is usually achieved using extra reducers that can compete with the CuII(O2) oxidizing species, causing a loss of efficiency. An alternative would consist of using a photosensitizer to control the reduction process. Association of a RuII photosensitizing subunit with a CuII pre-catalytic moiety assembled within a unique entity is shown to fulfill these requirements. In presence of a sacrificial electron donor and light, electron transfer occurs from the RuII center to CuII. In presence of dioxygen, this dyad proved to be efficient for sulfide, phosphine, and alkene catalytic oxygenation. Mechanistic investigations gave evidence about a predominant 3O2 activation pathway by the CuI moiety.
Electrochemically driven stereoselective approach tosyn-1,2-diol derivatives from vinylarenes and DMF
Chung, Da Sol,Park, Steve H,Lee, Sang-Gi,Kim, Hyunwoo
, p. 5892 - 5897 (2021)
We have developed an electrochemically driven strategy for the stereoselective synthesis of protectedsyn-1,2-diols from vinylarenes withN,N-dimethylformamide (DMF). The newly developed system obviates the need for transition metal catalysts or external oxidizing agents, thus providing an operationally simple and efficient route to an array of protectedsyn-1,2-diols in a single step. This reaction proceedsviaan electrooxidation of olefin, followed by a nucleophilic attack of DMF. Subsequent oxidation and nucleophilic capture of the generated carbocation with a trifluoroacetate ion is proposed, which gives rise predominantly to asyn-diastereoselectivity upon the second nucleophilic attack of DMF.
g-C3N4/metal halide perovskite composites as photocatalysts for singlet oxygen generation processes for the preparation of various oxidized synthons
Corti, Marco,Chiara, Rossella,Romani, Lidia,Mannucci, Barbara,Malavasi, Lorenzo,Quadrelli, Paolo
, p. 2292 - 2298 (2021/04/12)
g-C3N4/metal halide perovskite composites were prepared and used for the first time as photocatalysts forin situ1O2generation to perform hetero Diels-Alder, ene and oxidation reactions with suitable dienes and alkenes. The standardized methodology was made applicable to a variety of olefinic substrates. The scope of the method is finely illustrated and the reactions afforded desymmetrized hydroxy-ketone derivatives, unsaturated ketones and epoxides. Some limitations were also observed, especially in the case of the alkene oxidations, and poor chemoselectivity was somewhere observed in this work which is the first application of MHP-based composites forin situ1O2generation. The experimental protocol can be used as a platform to further expand the knowledge and applicability of MHPs to organic reactions, since perovskites offer a rich variety of tuning strategies which may be explored to improve reaction yields and selectivities.
Liquid-phase oxidation of olefins with rare hydronium ion salt of dinuclear dioxido-vanadium(V) complexes and comparative catalytic studies with analogous copper complexes
Maurya, Abhishek,Haldar, Chanchal
, (2021/02/26)
Homogeneous liquid-phase oxidation of a number of aromatic and aliphatic olefins was examined using dinuclear anionic vanadium dioxido complexes [(VO2)2(salLH)]? (1) and [(VO2)2(NsalLH)]? (2) and dinuclear copper complexes [(CuCl)2(salLH)]? (3) and [(CuCl)2(NsalLH)]? (4) (reaction of carbohydrazide with salicylaldehyde and 4-diethylamino salicylaldehyde afforded Schiff-base ligands [salLH4] and [NsalLH4], respectively). Anionic vanadium and copper complexes 1, 2, 3, and 4 were isolated in the form of their hydronium ion salt, which is rare. The molecular structure of the hydronium ion salt of anionic dinuclear vanadium dioxido complex [(VO2)2(salLH)]? (1) was established through single-crystal X-ray analysis. The chemical and structural properties were studied using Fourier transform infrared (FT-IR), ultraviolet–visible (UV–Vis), 1H and 13C nuclear magnetic resonance (NMR), electrospray ionization mass spectrometry (ESI-MS), electron paramagnetic resonance (EPR) spectroscopy, and thermogravimetric analysis (TGA). In the presence of hydrogen peroxide, both dinuclear vanadium dioxido complexes were applied for the oxidation of a series of aromatic and aliphatic alkenes. High catalytic activity and efficiency were achieved using catalysts 1 and 2 in the oxidation of olefins. Alkenes with electron-donating groups make the oxidation processes easy. Thus, in general, aromatic olefins show better substrate conversion in comparison to the aliphatic olefins. Under optimized reaction conditions, both copper catalysts 3 and 4 fail to compete with the activity shown by their vanadium counterparts. Irrespective of olefins, metal (vanadium or copper) complexes of the ligand [salLH4] (I) show better substrate conversion(%) compared with the metal complexes of the ligand [NsalLH4] (II).
Iodine-Initiated Dioxygenation of Aryl Alkenes Using tert-Butylhydroperoxides and Water: A Route to Vicinal Diols and Bisperoxides
Gao, Xiaofang,Lin, Jiani,Zhang, Li,Lou, Xinyao,Guo, Guanghui,Peng, Na,Xu, Huan,Liu, Yi
, p. 15469 - 15480 (2021/11/16)
An environment-friendly and efficient dioxygenation of aryl alkenes for the construction of vicinal diols has been developed in water with iodine as the catalyst and tert-butylhydroperoxides (TBHPs) as the oxidant. The protocol was efficient, sustainable, and operationally simple. Detailed mechanistic studies indicated that one of the hydroxyl groups is derived from water and the other one is derived from TBHP. Additionally, the bisperoxides could be obtained in good yields with iodine as the catalyst, Na2CO3 as the additive, and propylene carbonate as the solvent, instead.
SYNTHESIS AND APPLICATION OF CHIRAL SUBSTITUTED POLYVINYLPYRROLIDINONES
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Paragraph 0063, (2020/11/24)
Chiral polyvinylpyrrolidinone (CSPVP), complexes of CSPVP with a core species, such as a metallic nanocluster catalyst, and enantioselective oxidation reactions utilizing such complexes are disclosed. The CSPVP complexes can be used in asymmetric oxidation of diols, enantioselective oxidation of alkenes, and carbon-carbon bond forming reactions, for example. The CSPVP can also be complexed with biomolecules such as proteins, DNA, and RNA, and used as nanocarriers for siRNA or dsRNA delivery.
Regioselective biocatalytic self-sufficient Tishchenko-type reactionviaformal intramolecular hydride transfer
Buljubasic, Isa,Hall, Mélanie,Laggner, Olivia,Merusic, Kemal,Reiter, Tamara,Tassano, Erika,Vogel, Andreas
supporting information, p. 6340 - 6343 (2020/06/21)
A self-sufficient nicotinamide-dependent intramolecular bio-Tishchenko-type reaction was developed. The reaction is catalyzed by alcohol dehydrogenases and proceeds through formal intramolecular hydride transfer on dialdehydes to deliver lactones. Regioselectivity on [1,1′-biphenyl]-2,2′-dicarbaldehyde substrates could be controlledviathe electronic properties of the substituents. Preparative scale synthesis provided access to substituted dibenzo[c,e]oxepin-5(7H)-ones.
Syn-dihydroxylation of alkenes using a sterically demanding cyclic diacyl peroxide
Pilevar, Afsaneh,Hosseini, Abolfazl,Becker, Jonathan,Schreiner, Peter R.
, p. 12377 - 12386 (2019/10/11)
The syn-dihydroxylation of alkenes is a highly valuable reaction in organic synthesis. Cyclic acyl peroxides (CAPs) have emerged recently as promising candidates to replace the commonly employed toxic metals for this purpose. Here, we demonstrate that the structurally demanding cyclic peroxide spiro[bicyclo[2.2.1]heptane-2,4′-[1,2]dioxolane]-3′,5′-dione (P4) can be effectively used for the syn-dihydroxylation of alkenes. Reagent P4 also shows an improved selectivity for dihydroxylation of alkenes bearing β-hydrogens as compared to other CAPs, where both diol and allyl alcohol products compete with each other. Furthermore, the use of enantiopure P4 (labeled P4′) demonstrates the potential of P4′ for a metal-free asymmetric syn-dihydroxylation of alkenes.
Controlling Selectivity in Alkene Oxidation: Anion Driven Epoxidation or Dihydroxylation Catalysed by [Iron(III)(Pyridine-Containing Ligand)] Complexes
Tseberlidis, Giorgio,Demonti, Luca,Pirovano, Valentina,Scavini, Marco,Cappelli, Serena,Rizzato, Silvia,Vicente, Rubén,Caselli, Alessandro
, p. 4907 - 4915 (2019/08/30)
A highly reactive and selective catalytic system comprising Fe(III) and macrocyclic pyridine-containing ligands (Pc-L) for alkene oxidation by using hydrogen peroxide is reported herein. Four new stable iron(III) complexes have been isolated and characterized. Importantly, depending on the anion of the iron(III) metal complex employed as catalyst, a completely reversed selectivity was observed. When X=OTf, a selective dihydroxylation reaction took place. On the other hand, employing X=Cl resulted in the epoxide as the major product. The reaction proved to be quite general, tolerating aromatic and aliphatic alkenes as well as internal or terminal double bonds and both epoxides and diol products were obtained in good yields with good to excellent selectivities (up to 93 % isolated yield and d.r.=99 : 1). The catalytic system proved its robustness by performing several catalytic cycles, without observing catalyst deactivation. The use of acetone as a solvent and hydrogen peroxide as terminal oxidant renders this catalytic system appealing.
