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Enhancing Chemo- And Stereoselectivity in C-H Bond Oxygenation with H2O2by Nonheme High-Spin Iron Catalysts- And Role of Lewis Acid and Multimetal Centers
Spin states of iron often direct the selectivity in oxidation catalysis by iron complexes using hydrogen peroxide (H2O2) on an oxidant. While low-spin iron(III) hydroperoxides display stereoselective C-H bond hydroxylation, the reactions are nonstereoselective with high-spin iron(II) catalysts. The catalytic studies with a series of high-spin iron(II) complexes of N4 ligands with H2O2 and Sc3+ reported here reveal that the Lewis acid promotes catalytic C-H bond hydroxylation with high chemo- and stereoselectivity. This reactivity pattern is observed with iron(II) complexes containing two cis-labile sites. The enhanced selectivity for C-H bond hydroxylation catalyzed by the high-spin iron(II) complexes in the presence of Sc3+ parallels that of the low-spin iron catalysts. Furthermore, the introduction of multimetal centers enhances the activity and selectivity of the iron catalyst. The study provides insights into the development of peroxide-dependent bioinspired catalysts for the selective oxygenation of C-H bonds without the restriction of using iron complexes of strong-field ligands.
Das, Abhishek,Jana, Rahul Dev,Paine, Tapan Kanti
p. 5969 - 5979
(2021/05/04)

Catalytic hydrogenation of aromatic rings catalyzed by Pd/NiO
A simple and efficient heterogeneous palladium catalyst was prepared for aromatic ring hydrogenation. The catalyst was prepared by a reduction-deposition method and exhibited high activity and selectivity for the hydrogenation of a variety of substituted aromatic compounds to the corresponding cyclohexane and cyclohexanol derivatives with up to 99% yields. The catalyst was characterized by BET, TEM, XRD, XPS and ICP. Meanwhile the reusability of the catalyst was investigated, and it can be reused for several runs without significant deactivation.
Wang, Yanan,Cui, Xinjiang,Deng, Youquan,Shi, Feng
p. 2729 - 2732
(2014/01/06)

Synthesis of poly(decahydro-2-naphthyl methacrylate)s with different geometric structures and effects of side-group dynamics on polymer properties investigated by thermal and dynamic mechanical analyses and DFT calculations
We prepared the geometric isomers of decahydro-2-naphthols as the source materials for the synthesis of poly(decahydro-2-naphthyl methacrylate)s [poly(DNMA)-I, -II, -III, and -IV] including alicyclic ester groups with different geometric structures. The geometry and conformational dynamics of the decahydro-2-naphthyl moieties were investigated by NMR spectroscopy and DFT calculations. We synthesized each isomer of the methacrylic monomers, polymerized them, and investigated the optical, thermal, and mechanical properties of poly(DNMA)s with different isomer compositions. The Tg values of the poly(DNMA)s were in the following order: 139.3 C for poly(DNMA)-II 3/g, 1.489, and 42-44, respectively.
Ozaki, Anri,Sumita, Koha,Goto, Kunihiro,Matsumoto, Akikazu
p. 2941 - 2950
(2013/06/05)

An iron catalyst for oxidation of alkyl C-H bonds showing enhanced selectivity for methylenic sites
Many are called but few are chosen: A nonheme iron complex catalyzes the oxidation of alkyl C-H bonds by using H2O2 as the oxidant, showing an enhanced selectivity for secondary over tertiary C-H bonds (see scheme). Copyright
Prat, Irene,Gomez, Laura,Canta, Merce,Ribas, Xavi,Costas, Miquel
supporting information
p. 1908 - 1913
(2013/03/14)

Ytterbium triflate catalysed Meerwein-Ponndorf-Verley (MPV) reduction
Ytterbium triflate was shown to be effective in promoting the reduction of substituted aromatic and aliphatic aldehydes and ketones using isopropanol as the solvent and the reducing agent. The whole process furnished the desired adducts in 22-98% yield.
Mollica, Adriano,Genovese, Salvatore,Pinnen, Francesco,Stefanucci, Azzurra,Curini, Massimo,Epifano, Francesco
experimental part
p. 890 - 892
(2012/03/08)

Oxidative functional group transformations with hydrogen peroxide catalyzed by a divanadium-substituted phosphotungstate
A divanadium-substituted phosphotungstate TBA4[γ-PW 10O38V2(μ-OH)(μ-O)] (I, TBA = tetra-n-butylammonium) reacts with one equivalent H+ to form a bis-μ-hydroxo species [γ-PW10O38V 2(μ-OH)2]3- (I′) in organic media. The strong electrophilic oxidants such as [γ-PW10O 38V2(μ-OH)(μ-OOH)]3- (II) and [γ-PW10O38V2(μ-η2: η2-O2)]3- (III) are formed by the reaction of the bis-μ-hydroxo species with H2O2. In the presence of I and H+, H2O2-based oxidations such as (i) epoxidation of alkenes (17 examples including electron-deficient ones), (ii) hydroxylation of alkanes (11 examples), and (iii) oxidative bromination of alkenes, alkynes, and aromatics with Br- as a bromo source (12 examples including chlorination) chemo-, diastereo-, and regioselectively proceed to give the corresponding oxidized products in moderate to high yields with high efficiencies of H2O2 utilization.
Mizuno, Noritaka,Kamata, Keigo,Yamaguchi, Kazuya
scheme or table
p. 157 - 161
(2012/06/18)

Synthesis and Pseudomonas lipase inhibition study of stereoisomers of decahydro-2-naphthyl-N-n-butylcarbamate
(2S,4aR,8aS)-Cis,cis-, (2R,4aS,8aR)-cis,cis-, rac-cis,cis-, and rac-trans,cis-decahydro-2-naphthyl-N-n-butylcarbamates are synthesized from condensation of (2S,4aR,8aS)-cis,cis-, (2R,4aS,8aR)-cis,cis-, rac-cis,cis-, and rac-trans,cisdecahydro-2-naphthols, respectively, with n-butyl isocyanate in the presence of triethylamine in dichloromethane. Optically pure (2S,4aR,8aS)-(-)-and (2R,4aS,8aR)-(+)-cis,cis-decahydro-2-naphthols are resolved by the porcine pancreatic lipase-catalyzed acetylation of decahydro-2-naphthols with vinyl acetate in t-butyl methyl ether. Absolute configurations of (2S,4aR,8aS)-(-)-and (2R,4aS,8aR)-(+)-cis,cis-decahydro-2-naphthols are determined from the 19F NMR spectra of their Mosher's ester derivatives. (2S,4aR,8aR)-Trans,cis-and (2R,4aS,8aS)-trans,cis-decahydro-2- naphthols can't be resolved from the porcine pancreatic lipase-catalyzed acetylation of decahydro-2-naphthols with vinyl acetate in t-butyl methyl ether. For the inhibitory potency of Pseudomonas lipase, (2S,4aR,8aS)-cis,cis- decahydro-2-naphthyl-N-n-butylcarbamate is 3.5 times more potent than (2R,4aS,8aR)-cis,cis-decahydro-2-naphthyl-N-n-butylcarbamate; racemic cis,cis-decahydro-2-naphthyl-N-n-butylcarbamate is about the same with trans,cis-decahydro-2-naphthyl-N-n-butylcarbamate. These inhibitors also show similar effects on porcine pancreatic lipase.
Lin, Ming-Cheng,Shen, Yu-Fang,Lin, Gialih
scheme or table
p. 1168 - 1176
(2012/06/15)

Construction of a quaternary carbon at the carbonyl carbon of the cyclohexane ring
High SN2′ selectivity in the allylic substitution of cyclohexylidene ethyl picolinates with copper reagents prepared from RMgBr and CuBr·Me2S was realized by addition of ZnX2 (X = I, Br, Cl). Furthermore, ZnX2 accelerated the reaction with the bulky iPr reagent. The Royal Society of Chemistry 2010.
Kaneko, Yuki,Kiyotsuka, Yohei,Acharya, Hukum P.,Kobayashi, Yuichi
supporting information; experimental part
p. 5482 - 5484
(2010/10/04)

Efficient stereo- and regioselective hydroxylation of alkanes catalysed by a bulky polyoxometalate
Direct functionalization of alkanes by oxidation of C-H bonds to form alcohols under mild conditions is a challenge for synthetic chemistry. Most alkanes contain a large number of C-H bonds that present difficulties for selectivity, and the oxidants employed often result in overoxidation. Here we describe a divanadium-substituted phosphotungstate that catalyses the stereo- and regioselective hydroxylation of alkanes with hydrogen peroxide as the sole oxidant. Both cyclic and acyclic alkanes were oxidized to form alcohols with greater than 96% selectivity. The bulky polyoxometalate framework of the catalyst results in an unusual selectivity that can lead to the oxidation of secondary rather than the weaker tertiary C-H bonds. The catalyst also avoids wasteful decomposition of the stoichiometric oxidant, which can result in the production of hydroxyl radicals and lead to non-selective oxidation and overoxidation of the desired products.
Kamata, Keigo,Yonehara, Kazuhiro,Nakagawa, Yoshinao,Uehara, Kazuhiro,Mizuno, Noritaka
scheme or table
p. 478 - 483
(2010/09/17)

Efficient and Practical Arene Hydrogenation by Heterogeneous Catalysts under Mild Conditions
An efficient and practical arene hydrogenation procedure based on the use of heterogeneous platinum group catalysts has been developed. Rh/C is the most effective catalyst for the hydrogenation of the aromatic ring, which can be conducted in iPrOH under neutral conditions and at ordinary to medium H 2 pressures (10 atm). A variety of arenes such as alkylbenzenes, benzoic acids, pyridines, furans, are hydrogenated to the corresponding cyclohexyl and heterocyclic compounds in good to excellet yields. The use of Ru/C, less expensive than Rh/C, affords an effective and practical method for the hydrogenation of arenes including phenols. Both catalysts can be reused several times after simple filtration without any significant loss of catalytic activity.
Maegawa, Tomohiro,Akashi, Akira,Yaguchi, Kiichiro,Iwasaki, Yohei,Shigetsura, Masahiro,Monguchi, Yasunari,Sajiki, Hironao
experimental part
p. 6953 - 6963
(2010/02/28)

Rhodium/graphite-catalyzed hydrogenation of carbocyclic and heterocyclic aromatic compounds
Rhodium on graphite (Rh/Gr, C24Rh) was prepared by reaction of anhydrous rhodium trichloride with potassium graphite (C8K, 3 equivalents) and used as a heterogeneous catalyst for the hydrogenation of carbocyclic and heterocyclic aromatic compounds at room temperature and 1 atm of hydrogen pressure. The effect of substitution on the benzene ring was examined in a variety of derivatives, including those with alkyl, hydroxy, alkoxy, aryloxy, carboxy, amino, nitro, acyl, chloro, or functionalized alkyl groups. Reduction of carbonyl functions of aromatic aldehydes and ketones occurred with complete or partial cleavage of the benzylic C-O bond; this cleavage also occurred in the hydrogenation of benzylic alcohols and esters. Georg Thieme Verlag Stuttgart.
Falini, Giuseppe,Gualandi, Andrea,Savoia, Diego
experimental part
p. 2440 - 2446
(2010/02/27)

Compounds having protected hydroxy groups
The present invention relates to compounds with protected hydroxy groups of formula (I) These compounds are precursors for organoleptic agents, such as fragrances, and masking agents and for antimicrobial agents. When activated, the compounds of formula (I) are cleaved and form one or more organoleptic and/or antimicrobial compounds.
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(2008/06/13)

Beta-ketoester compounds
The beta-ketoesters of formula I are useful as precursors for organoleptic compounds, especially for flavors, fragrances and masking agents and antimicrobial compounds.
-
(2008/06/13)

Ketone precursors for organoleptic compounds
The invention discloses ketones of formula I: wherein, Y is an optionally substituted alkyl, cycloalkyl, or cycloalkylalkyl, wherein each alkyl group is straight or branched and each alkyl and cycloalkyl group is saturated or unsaturated; R1is hydrogen or a C1-6alkyl group that is substituted, saturated or unsaturated, straight or branched; A is a chromophoric substituted aromatic ring or ring system; n is an integer; and with the proviso that formula I is not 2-ethoxy-1-phenyl-ethanone. These compositions are useful for the delivery of organoleptic compounds, especially of flavors, fragrances, masking agents and antimicrobial compounds.
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(2008/06/13)

Role of the heteroatoms in the complex metal hydride reduction of 2-t- butyl-1,3-dioxan-5-one and 3-oxoquinolizidine: Comparison of their reactivity and stereochemistry with those of the corresponding carbocyclic compounds
The complex metal hydride reductions of 2-t-butyl-1,3-dioxan-5-one (1) and 3-oxoquinolizidine (3) are faster than those of the corresponding carbocyclic compounds, 4-t-butylcyclohexanone (2) and trans-2-decalone (4). The stereoselectivities were similar in the LiAlH4 reduction, but the heteracyclohexanones exhibited higher stereoselectivity with NaBH4. These facts are discussed in terms of the intramolecular orbital interaction.
Senda, Yasuhisa,Sakurai, Hiroshi,Itoh, Hiroki
p. 285 - 288
(2007/10/03)

Functional-Group-Directed Diastereoselective Hydrogenation of Aromatic Compounds
Diastereoselective liquid phase hydrogenation of a series of monosubstituted indane and tetralin substrates was studied on supported rhodium catalysts. Predominantly the cis-cis diastereomer, obtained by hydrogenation from the diastereoface opposite the substituent (at the stereogenic center), and the cis-trans diastereomer, obtained by hydrogenation from the diastereoface on the same side as the substituent, were formed. The diastereoselectivity between the two isomers was dependent on the steric repulsion or the electronic attraction of the substituent with the surface of the catalyst. The hydroxyl group did not exhibit a strong attraction (haptophilicity), and the cis-cis diastereomer was obtained as the major product. The amino group exhibited a very high haptophilicity, yielding primarily the cis-trans diastereomer. The diastereoselectivity obtained in the hydrogenation of all the substrates was influenced on addition of bases to the reaction mixture. In the case of alcoholic substrates, the selectivity to the cis-trans diastereomer could be substantially increased with alkaline hydroxide additives.
Ranade, Vidyadhar S.,Consiglio, Giambattista,Prins, Roel
p. 8862 - 8867
(2007/10/03)

The selective functionalization of saturated hydrocarbons. Part 46. An investigation of Udenfriend's system under Gif conditions
Under Gif conditions using ascorbic acid as reductant and oxygen as oxidant in pyridine, the selectivity for secondary hydrogen functionalization is exceptional. EDTA (ethylenediamine-tetra-acetic acid) is not needed as a ligand for iron.
Barton, Derek H.R.,Delanghe, Nathalie C.
p. 4471 - 4476
(2007/10/03)

Oxidation with the "O2 - H2O2 - Vauauium complex - Pyrazine-2-carboxylic acid" reagent 9. Oxidation of cyclohexene and decalin
The oxidation of cyclohexene with hydrogen peroxide catalyzed by a vanadium complex and pyrazine-2-carboxylic acid (PCA) in air results in the formation of cyclohex-2-enyl hydroperoxide as the main product and cyclohex-2-enol, cyclohex-2-enone, cyclohex-3-enyl hydroperoxide, cyclohex-3-enol, cyclohexanol, cyclohexane, and 1,2-epoxycyclohexane in lesser amounts. The composition of the products of oxidation of decalin isomers with the system in question is similar to those obtained in the photochemical oxidation with hydrogen peroxide in air and in the oxidation with air in the presence of anthraquinone. A proposed mechanism for the oxidation includes the initiation by hydroxyl radicals generated from hydrogen peroxide under the action of the V - PCA system.
Schuchardt,Guerreiro,Shul'pin
p. 247 - 252
(2007/11/27)

HYDROGENATION AND HYDROGENOLYSIS. XVII. THE SELECTIVITIES OF PLATINUM GROUP METALS IN CATALYTIC HYDROGENATION OF 2-NAPHTHOL AND TETRAHYDRO-2-NAPHTHOLS.
Catalytic hydrogenation of 2-naphthol (NL) with the six platinum metals has been studied in t-BuOH at 80 degree C and 4-5 MPa H//2 pressure. Selectivities for formation of 1,2,3,4- and 5,6,7,8-tetrahydro-2-naphthols (ac- and ar-TLs) have been determined by application of a kinetic equation. ar-TL was formed more predominantly than ac-TL over all the metals. The hydrogenation of ac- and ar-TLs has also been studied under the same conditions for comparison. The hydrogenation of NL and ar-TL was accompanied by extensive hydrogenolysis to give decalins over Os, Ir, and Pt, whereas the hydrogenolysis occurred only slightly over Ru, Rh, and Pd. In general the hydrogenolysis occurred to much lesser extents with ac-TL. The amounts of 2-decalone formed in hydrogenation of ar-TL have been determined by application of the kinetic equation.
Nishimura,Ohbuchi,Ikeno,Okada
p. 2557 - 2564
(2007/10/02)

Enzymic Resolution of (+/-)-axial-Alcohols via Asymmetric Hydrolysis of Corresponding Chloroacetates by Microorganisms
Asymmetric hydrolysis of chloroacetates of (+/-)-axial-alcohols (+/-)-neomenthol (2), (1RS,4aRS,8aSR)-decahydro-1-naphthol (6) by Trichoderma koningi gave (-)-(1S,3R,4R)-neomenthol (2) (54percent optical purity, o.p.) and (-)-(1R,4aR,8aS)-decahydro-1-naphthol (6) (66percent o.p.) with their enantiomeric chloroacetates.However, the chloroacetate of (2RS,4aRS,8aSR)-decahydro-2-naphthol (10) was hydrolyzed by T. koningi to give the (-)-alcohol (10) (12percent o.p.) with low enantioselectivity.
Oritani, Takayuki,Ichimura, Michio,Hanyu, Yoshifumi,Yamashita, Kyohei
p. 2613 - 2618
(2007/10/02)

Aliphatic Hydroxylation Catalyzed by Iron Porphyrin Complexes
The hydroxylation of unactivated alkanes has been observed in a catalytic system containing iodosylbenzene and various iron porphyrins.The yields and distributions of products have been found to be sensitive to the peripheral substitution pattern of the porphyrin.The oxidation of cyclohexane with chloro(5,10,15,20-tetra-o-tolylporphyrinato)iron(III) gave a 31percent yield of cyclohexanol and 6percent cyclohexanone based on iodosylbenzene.Two samples of Fe(TTP)ClCl with differing atropisomeric composition gave different product ratios.The hydroxylation of cycloheptane under these conditions and in the presence of bromotrichloromethane gave 24percent cycloheptanol and 18percent bromocycloheptane.Steric selectivity was observed by comparing the hydroxylation of cis-decalin with Fe(TPP)Cl, Fe(TTP)Cl, Fe(TNP)Cl, and Fe(TMP)Cl.The hydrogen-isotope effect for cyclohexane hydroxylation by Fe(TTP)Cl was found to be 12.9+/- 1.A mechanism for hydroxylation is proposed on the basis of these results that involves initial oxidation of the iron porphyrin, hydrogen atom abstraction from the alkane, and rapid collapse of this radical to give the product alcohol and to regenerate the iron(III) catalyst.
Groves, John T.,Nemo, Thomas E.
p. 6243 - 6248
(2007/10/02)

VANADIUM(V) PEROXO COMPLEXES. NEW VERSATILE BIOMIMETIC REAGENTS FOR EXPOXIDATION OF OLEFINS AND HYDROXYLATION OF ALKANES AND AROMATIC HYDROCARBONS.
Novel covalent vandium(V) oxo peroxo complexes of general formula VO(O//2)(O-N)LL prime and anionic complexes with the general formula left bracket VO(O//2)(Pic)//2 right bracket ** minus A** plus L were synthesized and characterized by physicochemical methods and X-ray crystallography. The crystal structure of VO(O//2)(Pic) multiplied by (times) 2H//2O (Ia) revealed a pentagonal-bipyramidal environment, with a significant hydrogen bonding between the peroxo moiety and the equatorial water molecule. Protonated type II complexes (A** plus equals H** plus ) are dissociated in an aqueous solution and have an acidic nature (pK//a equals 1. 8) but are undissociated in a nonprotic solution, with a presumably peracid-like oxohydroperoxo structure. It is shown that vanadium peroxo complexes are effective oxidants in nonprotic solvents under mild conditions. They transform olefins to epoxides and cleavage products in a nonsteoroselective fashion (cis-2-butene gave a mixture of cis and trans epoxides). More interestingly, they hydroxylate aromatic hydrocarbons to phenols and alkanes to alcohols and ketones.
Mimoun,Saussine,Daire,Postel,Fischer,Weiss
p. 3101 - 3110
(2007/12/18)

Model Systems for Cytochrome P450 Dependent Mono-oxygenases. Part 3. The Stereochemistry of Hydroxylation of cis- and trans-Decahydronaphthalene by Chemical Models for Cytochrome P450 Dependent Mono-oxygenases
The stereochemistry of hydroxylation of the tertiary C-H bonds of cis- and trans-decahydronaphthalene by seven chemical models for cytochrome P450 dependent mono-oxygenases has been studied.Oxidations by three of the model systems (H2O2-Fe2+-CH3CN, O2-Fe2+-2-mercaptobenzoic acid, and diazofluorene-hν-O2) are non-stereospecific giving the same ratio of cis- to trans-decahydronaphthalen-9-ol from each substrate.However, hydroxylations with pyridine N-oxide-hν show a partial retention of configuration and with trifluoroperacetic acid or with iron(III) porphyrins and iodosylbenzene the oxidations are >97percent stereospecific.The mechanism of these hydroxylations and their usefulness as models for the cytochrome P450 dependent mono-oxygenases are discussed.
Smith, John R. Lindsay,Sleath, Paul R.
p. 1165 - 1170
(2007/10/02)

SELECTIVITE DE LA REDUCTION D'α-ENONES POLYCYCLIQUES PAR LES BOROHYDRURES: EFFET DE L'ADDITION DE TETRAMETHYL-ETHYLENEDIAMINE AU BOROHYDRURE DE TETRABUTYLAMMONIUM
Δ1,9octalone, Δ1,9-10-methyl octalone and testosterone were reduced by NBu4BH4, alone or in the presence of tetramethylethylenediamine (TMEDA), in THF and in toluene.With TMEDA, the first step of the reduction is the regioselective 1,4 attack by BH4(1-) which leads either to the saturated ketones or to the corresponding saturated alcohols.The results observed under different conditions were interpreted by the intervention of various reductive species: diborane, enoxyborohydrides in the absence of TMEDA, amine-borane in its presence.
D'incan, E.,Loupy, A.,Maia, A.,Seyden-Penne, J.,Viout, P.
p. 2923 - 2927
(2007/10/02)

BOROHYDRIDE REDUCTION OF Δ1,9 2-OCTALONE : CATION INFLUENCE AND AMINE ADDITION EFFECTS
Proton removal of Δ1,9 2-octalone occurs when reacted with NBu4BH4 in aprotic solvents while 1-2 reduction is important with NaBH4 in THF.Both are inhibited when NaBH4 reduction is performed in the presence of amines, leading thus to highly selective formation of saturated alcohols.
D'Incan, E.,Loupy, A.,Maia, A.
p. 941 - 944
(2007/10/02)

Sand-supported Organic Reactions: NaBH4 Reduction of Carbonyl Compounds
'Fontainebleau sand' is an efficient support for the NaBH4 reduction of carbonyl compounds in the absence of organic solvent.
Bram, Georges,d'Incan, Esther,Loupy, Andre
p. 1066 - 1067
(2007/10/02)