- Long tailed cage amines: Synthesis, metal complexation, and structure
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The generation of amphiphiles derived from macrobicyclic hexamines of the "sarcophagine" class can be prepared through efficient and selective reactions involving the reductive alkylation, using long-chain aldehydes, of amino-functionalised sarcophagines when bound to Cu(ii) or Mg(ii). The Mg(ii) pathway is particularly convenient for the ultimate isolation of the free ligands, which can then be used to form metalloamphiphiles with a variety of metal ions. Structural studies have been made of one of the free (protonated) ligands and some of their complexes.
- Dittrich, Birger,Harrowfield, Jack M.,Koutsantonis, George A.,Nealon, Gareth L.,Skelton, Brian W.
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- Synthesis and preferred conformations of all regio- and diastereoisomeric methyl 2,3-fluorohydroxyalkanoates
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Selective syntheses of enantiopure regio- and diastereomeric methyl 2,3-fluoro-hydroxyalkanoates via four different routes employing two types of fluorination reagents are reported. The anti- and syn-3-fluoro-2- hydroxyalkanoates 1 and 3 were prepared by treating the corresponding epoxides with Olah's reagent (Py·9HF). Cyclic sulfates prepared from the enantiomeric diols were ring-opened with TBAF to give the anti- and syn-2-fluoro-3-hydroxyalkanoates 2 and 4. Thestereochemical analysis was performed mainly by NMR spectroscopy. Applying DFT/B3LYP and SCS-MP2 quantum chemical methods, the coupling constants and relative energies of conformers were calculated. Solvent effects were considered using the COSMO continuum model. Regio- and stereoselective ring opening of enantio-pure epoxides or cyclic sulfates with pyridine·9HF or TBAF delivers anti- or syn-configurated 3-fluoro-2-hydroxy- or 2-fluoro-3-hydroxyalkanoates, respectively. The relative energies of conformers were calculated by quantum chemical methods. Those of 3-fluoro-2-hydroxy isomers are influenced by intramolecular O-H·O=C hydrogen bonds, while the regioisomers show close O-H·F-C contacts. Copyright
- Husstedt, Wibke S.,Wiehle, Susanne,Stillig, Christian,Bergander, Klaus,Grimme, Stefan,Haufe, Guenter
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- Flexible, polymer-supported synthesis of sphingosine derivatives provides ceramides with enhanced biological activity
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A polymer-supported route for the synthesis of sphingosine derivatives is presented based on the C-acylation of polymeric phosphoranylidene acetates with an Fmoc-protected amino acid. The approach enables the flexible variation of the sphingosine tail through a deprotection-decarboxylation sequence followed by E-selective Wittig olefination cleavage. d-Erythro-sphingosine analogs have been synthesized by diastereoselective reduction of the keto group employing LiAlH(O-tBu)3as reducing agent. The effect of ceramides and keto-ceramides on the proliferation of three cancer cell lines HEP G-2, PC-12 and HL-60 was investigated and a ceramide containing an aromatic sphingosine tail was identified as being most active.
- El-Dahshan, Adeeb,Al-Gharabli, Samer I.,Radetzki, Silke,Al-Tel, Taleb H.,Kumar, Pradeep,Rademann, J?rg
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- Copper-Catalyzed Asymmetric Conjugate Additions of Bis(pinacolato)diboron and Dimethylzinc to Acyl- N-methylimidazole Michael Acceptors: A Highly Stereoselective Unified Strategy for 1,3,5,... n (OH, Me) Motif Synthesis
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A unified strategy for the construction of prevalent 1,3,5,...n (OH, Me) motifs based on consecutive copper-catalyzed asymmetric conjugate borylation (ACB) and methylation (ACA) reactions involving α,β-unsaturated 2-acyl-N-methylimidazoles is described. Good yields and high diastereoselectivities have been obtained in ACA and ACB reactions for both matched and mismatched pairs as illustrated in the synthesis of syn/anti and anti/anti (Me, OTBS, Me) and (OH, OTBS, Me) motifs.
- Lauberteaux, Jimmy,Crévisy, Christophe,Baslé, Olivier,De Figueiredo, Renata Marcia,Mauduit, Marc,Campagne, Jean-Marc
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- Protolichesterinic acid derivatives: α-Methylene-γ-lactones as potent dual activators of PPARγ and Nrf2 transcriptional factors
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PPARγ and Nrf2 are important transcriptional factors involved in many signaling pathways, especially in the anti-infectious response of macrophages. Compounds bearing a Michael acceptor moiety are well known to activate such transcriptional factors, we thus evaluated the potency of α,β- unsaturated lactones synthesized using fluorous phase organic synthesis. Compounds were first screened for their cytotoxicity in order to select lactones for PPARγ and Nrf2 activation evaluation. Among them, two α-methylene-γ-lactones were identified as potent dual activators of PPARγ and Nrf2 in macrophages.
- Le Lamer, Anne-Cécile,Authier, Hélène,Rouaud, Isabelle,Coste, Agnès,Boustie, Jo?l,Pipy, Bernard,Gouault, Nicolas
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- Synthesis and characterization of a Ni nanoparticle stabilized on Ionic liquid-functionalized magnetic Silica nanoparticles for tandem oxidative reaction of primary alcohols
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In this research, preparation of the magnetic nanoparticle, coating by a silica shell using (3-aminopropyl) triethoxysilane and synthesis of a novel sulfonic acid-substituted imidazolium-based ionic liquid onto the surface of these particles via a multi-component reaction, is described. The functionalized nanoparticles was loaded by Ni nanoparticles and characterized by means of techniques such as XRD, FTIR, SEM, EDX, TEM, TGA and ICP-OES. The nanostructures have spherical shapes that ranged in size from 80 to 100?nm. The catalytic activity of these nanoparticles was tested in aerobic oxidation of primary alcohols that showed good performance in the wide range of primary alcohols in water at mild reaction conditions. As a second step of this work, the tandem oxidative synthesis of alkylacrylonitriles and bisindolylmethanes were investigated using primary alcohols under oxidation conditions. This catalyst system can be recovered using external magnet and reused for five consecutive cycles without significantly less of its activity.
- Hosseinzadeh-Khanmiri, Rahim,Kamel, Yaser,Keshvari, Zahra,Mobaraki, Ahmad,Shahverdizadeh, Gholam Hossein,Vessally, Esmail,Babazadeh, Mirzaagha
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- Oxidation of long-chain alcohols to aldehydes by the dipyridine chromic anhydride complex
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The oxidation of alcohols by the dipyridine chromic anhydride complex is judged to be most suitable for the preparation of long-chain aliphatic aldehydes. Thus, cis-9-octadecenol is oxidized in 93% yield within 30 min at room temperature with no detectabl
- Valicenti,Holman
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- Selectivity control in oxidation of 1-tetradecanol on supported nano Au catalysts
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Selective oxidation of tetradecanol, a model higher fatty alcohol, on Au/CeO2-Al2O3 catalyst has been investigated to assess the factors that control selectivity. The analysis of the effect of operation conditions (temperature, run time and alcohol/metal (A/M) ratio) on catalytic performance revealed a quite complex reaction network, in which acid formation starts only after a certain level of conversion is reached. This level depends linearly on the total support surface available, indicating that it must be saturated by species generated by the reaction itself to allow acid formation to start. Addition of water to reaction medium did not modify this level, indicating that such species is not adsorbed water, as previously hypothesized, but probably spilled over hydrogen species. The resulting drastic change in the selectivity trends makes the ratio A/M a critical factor to control selectivity to aldehyde and to acid. Selectivity to ester is less sensible to operation parameters. It is noteworthy that aldehyde yields up to 27% with 90% selectivity, and acid yields up to 40% with 81% selectivity can be reached by proper selection of operation parameters.
- Martínez-González,Ivanova, Svetlana,Domínguez, María I.,Cortés Corberán
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- Chiral geminal disilyl alkane compound, synthesis method and applications thereof
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The present invention discloses a chiral geminal disilyl alkane compound, which is represented by a formula V, wherein * represents a chiral carbon atom in the formula V. The invention discloses a synthesis method of the chiral geminal disilyl alkane compound, wherein the synthesis method comprises: carrying out a reaction in the presence of a reducing agent by using alkyne represented by a formula I, dihydrosilane represented by a formula II and trihydrosilane represented by a formula III as raw materials and using Xantphos-CoBr2 and a chiral CoX2-OIP complex as catalysts under an inert gas to prepare the chiral geminal disilyl alkane compound represented by the formula V. According to the present invention, the method has characteristics of mild reaction condition, simple operation, highatomic economy, no requirement of the addition of any other toxic transition metals (such as ruthenium, rhodium, palladium and the like) salts, high yield and high enantioselectivity, and has great practical value in the synthesis of drugs and materials, wherein the yield is generally 50-85%, and the enantioselectivity is generally 93-99%. The formulas I, II, III and V are defined in the specification.
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Paragraph 0204; 0205; 0206; 0207; 0209
(2019/01/14)
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- Racemic gem disilyl alkane compound containing four silicon-hydrogen bonds, and sybthesis method and application of compound
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The invention discloses a racemic gem disilyl alkane compound containing four silicon-hydrogen bonds. The compound is as shown in a formula IV. The invention further discloses a synthesis method of the racemic gem disilyl alkane compound. The synthesis method comprises the following step of carrying out a reaction by taking alkyne as shown in a formula I and trihydrosilane as shown in a formula IIas raw materials and taking a chiral CoX-IIP complex as a catalyst in the presence of a reducing agent to obtain the racemic gem disilyl alkane compound containing four silicon-hydrogen bonds, wherein the compound is as shown in the formula IV. The method disclosed by the invention has mild reaction conditions, is simple and convenient to operate and has high atom economy. In addition, the reaction does not need addition of any salts of toxic transition metals (such as ruthenium, rhodium, palladium and the like), and the method has a relatively large practical application value in synthesis of medicines and materials. In addition, the reaction has a medium to excellent yield (51-99%) and high area selectivity (10:1-19:1, most parts larger than 19:1).
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Paragraph 0263-0268; 0269
(2019/05/15)
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- Total Synthesis of the Proposed Structure of Mycobactin J
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The total synthesis of the proposed structure of mycobactin J (MJ), a metabolite of Mycobacterium tuberculosis, is presented. The highlights of the synthesis include a careful control of the Z-stereochemistry of the unsaturated long chain fatty acid, a biomimetic construction of the oxazoline building block and the carriage of an unprotected phenol throughout the synthesis.
- Ghosh, Chiranjit,Pal, Sujit,Patel, Akanksha,Kapur, Manmohan
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supporting information
p. 6511 - 6515
(2018/10/20)
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- Highly practical and efficient preparation of aldehydes and ketones from aerobic oxidation of alcohols with an inorganic-ligand supported iodine catalyst
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Herein, we divulge an efficient protocol for aerobic oxidation of alcohols with an inorganic-ligand supported iodine catalyst, (NH4)5[IMo6O24]. The catalyst system is compatible with a wide range of groups and exhibits high selectivity, and shows excellent stability and reusability, thus serving as a potentially greener alternative to the classical transformations.
- Zhang, Mengqi,Zhai, Yongyan,Ru, Shi,Zang, Dejin,Han, Sheng,Yu, Han,Wei, Yongge
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supporting information
p. 10164 - 10167
(2018/09/13)
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- NOVEL SUGAR DERIVATIVE GELATORS
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A novel gelator including a sugar derivative; a gelator including a compound of Formula (1) or Formula (2): wherein R1 is a linear or branched alkyl group having a carbon atom number of 9 to 20, a cyclic alkyl group having a carbon atom number of 13 to 20, or a linear or branched alkenyl group having a carbon atom number of 9 to 20, R2 is a hydrogen atom, a linear or branched alkyl group having a carbon atom number of 1 to 10, or an aryl group optionally having a substituent, and R3 and R4 are hydroxy groups.
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Paragraph 0197; 0198; 0199
(2018/08/12)
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- Sequential reactions from catalytic hydroformylation toward the synthesis of amino compounds
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Different families of new amino compounds were efficiently synthesized, through optimized sequential processes, involving rhodium catalyzed hydroformylation as the key step. The selection of appropriate hydroformylation catalytic systems and reaction conditions allowed obtaining aldehydes derived from several n-alkyl olefins, cholest-4-ene and 3-vinyl-1H-indole, which were subsequently transformed, in one-pot, in to α-amino acids via hydroformylation/Strecker reaction, and in to tertiary amines via hydroaminomethylation, with excellent yields.
- Almeida, Ana R.,Carrilho, Rui M.B.,Peixoto, Andreia F.,Abreu, Artur R.,Silva, Artur,Pereira, Mariette M.
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supporting information
p. 2389 - 2395
(2017/04/03)
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- Bioinspired aerobic oxidation of alcohols with a bifunctional ligand based on bipyridine and TEMPO
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A novel bioinspired bifunctional ligand incorporating metal-binding site and stable free radical has been synthesized. The catalytic system obtained from the bifunctional ligand with copper(i) iodide in the presence of N-methylimidazole is highly efficient for the oxidation of a broad range of primary benzylic, allylic, alkynyl, aliphatic alcohols and secondary benzylic alcohols to the corresponding aldehydes and ketones in good to excellent yields. The catalyst system exhibits broad functional-group compatibility. The reaction is carried out in acetonitrile as solvent under air balloon at room temperature. The catalyst system features excellent activity for primary aliphatic alcohol oxidation and a high chemoselective oxidation of primary alcohols over the secondary alcohols. This oxidation process is readily amenable to larger-scale application. The interaction of the different components in the reaction mixtures was studied by UV-visible spectroscopy. The data indicated that Cu(i) existed throughout the reaction. A plausible mechanism of the catalytic cycle is proposed.
- Wang, Lianyue,Bie, Zhixing,Shang, Sensen,Lv, Ying,Li, Guosong,Niu, Jingyang,Gao, Shuang
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p. 35008 - 35013
(2016/05/19)
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- Iron/ABNO-Catalyzed Aerobic Oxidation of Alcohols to Aldehydes and Ketones under Ambient Atmosphere
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We report a new Fe(NO3)3·9H2O/9-azabicyclo[3.3.1]nonan-N-oxyl catalyst system that enables efficient aerobic oxidation of a broad range of primary and secondary alcohols to the corresponding aldehydes and ketones at room temperature with ambient air as the oxidant. The catalyst system exhibits excellent activity and selectivity for primary aliphatic alcohol oxidation. This procedure can also be scaled up. Kinetic analysis demonstrates that C-H bond cleavage is the rate-determining step and that cationic species are involved in the reaction.
- Wang, Lianyue,Shang, SenSen,Li, Guosong,Ren, Lanhui,Lv, Ying,Gao, Shuang
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p. 2189 - 2193
(2016/03/15)
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- A functionalized phosphine merit preparation of ionic liquids and its application in the hydroformylation reaction
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The invention relates to synthesis of first-class phosphorus functionalized polyether alkyl guanidinium ionic liquid, and an application of the first-class phosphorus functionalized polyether alkyl guanidinium ionic liquid in a homogeneous catalytic reaction. The functionalized ionic liquid of such class can be easily prepared by an ion exchange reaction between the polyether alkyl guanidinium ionic liquid and sulfonic acid type water soluble phosphine ligand. The designed phosphorus functionalized ionic liquid can be applied to organic reactions, including hydroformylation, hydroesterification, hydrocarboxylation and catalytic hydrogenation under the catalyzing of a transition metal; the dosage of the ionic liquid used in the catalytic reaction can be decreased; the activity of the catalytic reaction can be improved; a catalyst can be separated and cycled simply and conveniently.
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Paragraph 0077; 0078; 0079
(2017/11/08)
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- Development of an acid ceramidase activity-based probe
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Acid ceramidase is responsible for the ultimate step in the catabolism of (glyco)sphingolipids by hydrolysis of ceramide into sphingosine and free fatty acid. Deficiency in acid ceramidase is the molecular basis of Farber disease. Here we report the synthesis and characterization of an activity-based acid ceramidase probe.
- Ouairy, Cécile M. J.,Ferraz, Maria J.,Boot, Rolf G.,Baggelaar, Marc P.,Van Der Stelt, Mario,Appelman, Monique,Van Der Marel, Gijsbert A.,Florea, Bogdan I.,Aerts, Johannes M. F. G.,Overkleeft, Herman S.
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supporting information
p. 6161 - 6163
(2015/04/14)
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- A simple procedure for the oxidation of alcohols using [bis(acetoxy)iodo]benzene and a catalytic amount of bromide ions in ethyl acetate
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Abstract Primary and secondary benzylic alcohols and secondary aliphatic alcohols were oxidized to the corresponding aldehydes and ketones by using [bis(acetoxy)iodo]benzene (BAIB) and a catalytic amount of bromide ions, from tetrabutylammonium bromide or KBr, in ethyl acetate. The catalytic role of the bromide ions was also highlighted in the oxidation of primary aliphatic alcohols and secondary allylic alcohols carried out in the presence of 1 mol% TEMPO.
- Salvo, Anna Maria Pia,Campisciano, Vincenzo,Beejapur, Hazi Ahmad,Giacalone, Francesco,Gruttadauria, Michelangelo
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p. 1179 - 1184
(2015/06/02)
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- Exploring the synthetic applicability of a new carboxylic acid reductase from Segniliparus rotundus DSM 44985
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A new carboxylic acid reductase (CAR) gene from Segniliparus rotundus DSM 44985 was overexpressed in Escherichia coli. The recombinant enzyme exhibited high activity toward a variety of aromatic and aliphatic carboxylic acids. Especially, it effectively reduced 4-hydroxybenzoic acid (8a) and 4-nitrobenzoic acid (19a), toward which the known Nocardia CAR exhibited no or little activity. The recombinant E. coli cells co-expressing the Segniliparus CAR and Nocardia PPTase genes catalyzed the reductions of vanillic acid (20a) and 3,4-dihydroxyphenylacetic acid (25a) to give vanillyl alcohol (20c) and 3-hydroxytyrosol (25c) with high yield, respectively. The endogenous aldehyde reductases of E. coli should be responsible for the further reduction of the produced aldehydes. These results demonstrated that Segniliparus CAR was a useful addition to the biocatalyst tool-box for the reduction of carboxylic acids and might find applications in the synthesis of valuable bio-based chemicals from renewable resources.
- Duan, Yitao,Yao, Peiyuan,Chen, Xi,Liu, Xiangtao,Zhang, Rui,Feng, Jinhui,Wu, Qiaqing,Zhu, Dunming
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- Palladium-catalyzed formal hydroacylation of allenes employing carboxylic anhydrides and hydrosilanes
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The formal hydroacylation reaction of allenes has been developed employing carboxylic anhydrides as acyl sources and hydrosilanes as reducing reagents in the presence of a commercially available palladium complex as a catalyst. The reaction affords α,β-unsaturated ketones regio- and stereoselectively. The similar catalyst system is also effective for the reduction of carboxylic anhydrides to the corresponding aldehydes employing hydrosilanes.
- Fujihara, Tetsuaki,Hosomi, Takuro,Cong, Cong,Hosoki, Tomoya,Terao, Jun,Tsuji, Yasushi
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supporting information
p. 4570 - 4574
(2015/03/30)
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- NEW LIGANDS FOR TARGETING OF S1P RECEPTORS FOR IN VIVO IMAGING AND TREATMENT OF DISEASES
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The present invention relates to novel compounds of formulae (I) and (II) which are useful in the prevention, treatment and diagnosis, in vivo diagnosis of diseases or disorders related to S1P receptors, in particular, in diseases which are connected to the regulatory function of sphingosine-1-phosphate (S1P) and its analogues, such as inflammation, pain, autoimmune diseases and cardiovascular diseases.
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Paragraph 0353; 0354; 0355; 0356; 0357; 0358
(2014/06/25)
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- Formal total synthesis of stevastelins B and B3
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The formal total synthesis of stevastelins B and B3 (2 and 4, resp.) have been accomplished employing a highly enantiomerically controlled Lewis acid catalyzed non-aldol approach to obtain the syn aldol product and temperature controlled hydroboration oxidation reaction to construct four consecutive stereogenic centers. The other key reactions include Sharpless asymmetric epoxidation, macrolactonization, and macrolactamization towards building the core skeleton 2 and 4. Copyright
- Singh Yadav, Jhillu,Sekhar Mandal, Satadru,Srihari, Pabbaraja
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p. 669 - 688
(2014/06/09)
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- METHODS FOR THE SYNTHESIS OF SPHINGOMYELINS AND DIHYDROSPHINGOMYELINS
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The present invention includes methods for the synthesis of sphingomyelins and dihydrosphingomyelins. The present invention also includes methods for the synthesis of sphingosines and dihydrosphingosines. The present invention further includes methods for the synthesis of ceramides and dihydroceramides.
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Paragraph 0237
(2014/09/30)
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- METHODS FOR THE SYNTHESIS OF SPHINGOMYELINS AND DIHYDROSPHINGOMYELINS
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The present invention includes methods for the synthesis of sphingomyelins and dihydrosphingomyelins. The present invention also includes methods for the synthesis of sphingosines and dihydrosphingosines. The present invention further includes methods for the synthesis of ceramides and dihydroceramides.
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Paragraph 00202
(2014/09/29)
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- 4-Benzamido-TEMPO catalyzed oxidation of a broad range of alcohols to the carbonyl compounds with NaBrO3 under mild conditions
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4-Benzamido-TEMPO catalyzed oxidation system for conversion of a wide range of alcohols to the aldehydes or ketones with NaBrO3 under room temperature conditions has been developed. The credible, operationally convenient and economical, and condition mild oxidation protocol is particularly of interest in laboratory and in fine chemicals manufacture. 4-Benzamido-TEMPO catalyzed oxidation system for conversion of a wide range of alcohols to the aldehydes or ketones with NaBrO3 as oxidant under room temperature conditions has been developed. Copyright
- Shen, Jiaxuan,Sun, Jiangkai,Qin, Shuangshuang,Chu, Changhu,Liu, Renhua
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p. 405 - 409
(2014/06/10)
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- Heterogeneous selective oxidation of fatty alcohols: Oxidation of 1-tetradecanol as a model substrate
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s Selective oxidation of fatty alcohols, i.e., linear long-chain alkanols, has been scarcely investigated to date, despite its potential application in high value chemical's production. We report for the first time the liquid phase heterogeneous oxidation of 1-tetradecanol, used as a model molecule for fatty alcohols, according to green chemistry principles by using a Au/CeO2-Al2O3 catalyst and O2 as oxidant at normal pressure. High selectivity to tetradecanal (ca. 80%) or to tetradecanoic acid (60-70%) are reached at medium conversion (up to 38%), depending on the reaction conditions used. Comparison with similar tests of 1-octanol oxidation shows that the increase of the carbon chain length decreases the alcohol conversion and the formation of ester, probably due to a greater steric effect.
- Corberán, Vicente Cortés,Gómez-Avilés, Almudena,Martínez-González, Susana,Ivanova, Svetlana,Domínguez, María I.,González-Pérez, María Elena
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- Oxidation of plasmalogen, low-density lipoprotein and raw 264.7 cells by photoactivatable atomic oxygen precursors
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The oxidation of lipids by endogenous or environmental reactive oxygen species (ROS) generates a myriad of different lipid oxidation products that have important roles in disease pathology. The lipid oxidation products obtained in these reactions are dependent upon the identity of the reacting ROS. The photoinduced deoxygenation of various aromatic heterocyclic oxides has been suggested to generate ground state atomic oxygen (O[3P]) as an oxidant; however, very little is known about reactions between lipids and O(3P). To identify lipid oxidation products arising from the reaction of lipids with O(3P), photoactivatable precursors of O( 3P) were irradiated in the presence of lysoplasmenylcholine, low-density lipoprotein and RAW 264.7 cells under aerobic and anaerobic conditions. Four different aldehyde products consistent with the oxidation of plasmalogens were observed. The four aldehydes were: tetradecanal, pentadecanal, 2-hexadecenal and hexadecanal. Depending upon the conditions, either pentadecanal or 2-hexadecenal was the major product. Increased amounts of the aldehyde products were observed in aerobic conditions. The photodeoxygenation of dibenzothiophene S-oxide has been suggested to generate ground state atomic oxygen (O[3P]). The reactivity of the putative O(3P) is distinct from other reactive oxygen species (ROS) and little is known about its reactivity with lipids and other biomolecules. In this work, exposure of low-density lipoprotein (LDL) to O(3P) yielded four aldehyde products. The same aldehydes were observed after the oxidation of an isolated plasmalogen by O(3P).
- Bourdillon, Max T.,Ford, Benjamin A.,Knulty, Ashley T.,Gray, Colleen N.,Zhang, Miao,Ford, David A.,McCulla, Ryan D.
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p. 386 - 393
(2014/04/03)
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- Iron oxide catalyzed reduction of acid chlorides to aldehydes with hydrosilanes
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Iron-catalyzed reduction of acid chlorides to the corresponding aldehydes with a hydrosilane as a reducing agent has been developed. A simple mixture of a commercially available iron oxide (FeO) and tris(2,4,6-trimethoxyphenyl) phosphine (TMPP) as a catalyst realized the reduction of acid chlorides to the corresponding aldehydes under mild reaction conditions.
- Cong, Cong,Fujihara, Tetsuaki,Terao, Jun,Tsuji, Yasushi
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- NEW LIGANDS FOR TARGETING OF S1P RECEPTORS FOR IN VIVO IMAGING AND TREATMENT OF DISEASES
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The present invention relates to novel compounds of formulae (I) and (II) which are useful in the prevention, treatment and diagnosis, in vivo diagnosis of diseases or disorders related to S1P receptors, in particular, in diseases which are connected to the regulatory function of sphingosine-1-phosphate (S1P) and its analogues, such as inflammation, pain, autoimmune diseases and cardiovascular diseases.
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Page/Page column 44-45
(2013/03/26)
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- Concise synthesis of (+)-serinolamide A
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Serinolamide A, isolated from a species of marine cyanobacteria, exhibits a moderate agonist effect and selectivity for the CB1 cannabinoid receptor, which is unusual for marine natural products. Herein, we reported a highly efficient enantiospecific first total synthesis of (+)-serinolamide A from l-serine in nine steps with 30% overall yield. The synthesis method provides a facile, practicable, and economical approach for the preparation of other similar endocanabinoid lipids.
- Gao, Ya-Ru,Guo, Shi-Huan,Zhang, Zhuan-Xiang,Mao, Shuai,Zhang, Yan-Lei,Wang, Yong-Qiang
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p. 6511 - 6513
(2013/11/19)
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- Practical one-pot sequence for the asymmetric synthesis of 1,2 diols from primary alcohols
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A practical one-pot three-step sequence is reported for the asymmetric synthesis of α-benzoyloxylated alcohols from primary alcohols. Good overall yields (36-52%) and enantioselectivities (91-94% e.e.) are obtained using a commercial organocatalyst in the key oxylation reaction. A simple modification in the protocol allows the formation of enantioenriched γ-benzoyloxylated α,β-unsaturated ester from alcohol. Synthetic utility has been harnessed to the easy preparation of (-)-γ-octalactone from hexan-1-ol.
- Hermange, Philippe,Portalier, Fran?ois,Thomassigny, Christine,Greck, Christine
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supporting information
p. 1052 - 1055
(2013/04/10)
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- 3-(2-AMINO-ETHYL)-ALKYLIDENE)-THIAZOLIDINE-2,4-DIONE AND 1-(2-AMINO-ETHYL)-ALKYLIDENE-1,3-DIHYDRO-INDOL-2-ONE DERIVATIVES AS SELECTIVE SPHINGOSINE KINASE 2 INHIBITORS
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3-(2-amino-ethyl)-5-[3-(4-substituted-phenyl)-alkylidene)-thiazolidine-2,4-dione and l-(2-amino-ethyl)-3-alkylidene-l,3-dihydro-indol-2-one and derivatives thereof are provided for use as selective SphK2 inhibitors and for use in the treatment of human diseases, such as cancer.
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Page/Page column 28
(2013/08/28)
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- Palladium-catalyzed reduction of carboxylic acids to aldehydes with hydrosilanes in the presence of pivalic anhydride
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A palladium catalyst system that allows the reduction of carboxylic acids to the corresponding aldehydes with hydrosilanes as reducing agent and pivalic anhydride as an indispensable reagent has been developed. A simple mixture of commercially available bis(dibenzylideneacetone)palladium(0) [Pd(dba) 2], tri(para-tolyl)phosphane and methylphenylsilane realized the reduction of various aliphatic carboxylic acids as well as benzoic acids to aldehydes in good to high yields. Copyright
- Fujihara, Tetsuaki,Cong, Cong,Terao, Jun,Tsuji, Yasushi
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supporting information
p. 3420 - 3424
(2013/12/04)
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- AMIDO-FLUOROPHOSPHITE COMPOUNDS AND CATALYSTS
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Amido-fluorophosphite compounds and catalyst systems comprising at least one amido-fluorophosphite ligand compound in combination with a transition metal are described. Moreover, the use of amido-fluorophosphite containing catalysts for transition metal catalyzed processes, especially to the hydroformylation of various olefins to produce aldehydes are also described.
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Page/Page column 26
(2013/03/26)
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- Spiralisones A-D: Acylphloroglucinol hemiketals from an Australian marine brown alga, Zonaria spiralis
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An intertidal sample of the Australian marine brown alga, Zonaria spiralis, exhibited promising kinase inhibitory and antibacterial activity. Chemical analysis returned six phloroglucinol-derived lipids, the new hemiketal spiralisones A-D (1-4) and the known chromones 5-6, and the known norsesquiterpenoid apo-9′-fucoxanthinone (7). Structures 1-7 were assigned on the basis of detailed spectroscopic analysis, biosynthetic considerations and total synthesis. Spiralisones undergo facile acid-mediated dehydration to yield the corresponding chromones, revealing for the first time that brown algal chromones may be handling artifacts rather than natural products. Hemiketals 1 and 2, and chromone 6, displayed inhibitory activity against the neurodegenerative disease kinase targets CDK5/p25, CK1δ and GSK3β, while hemiketals 1, 3 and 4, and chromone 6, displayed growth inhibitory activity against the Gram-positive bacteria Bacillus subtilis (ATCC 6051 and 6633). The promising kinase inhibitory and antibacterial properties of the Z. spiralis extract were attributed to the cumulative effect of many moderately potent phloroglucinol-derived lipid co-metabolites. The Royal Society of Chemistry 2012.
- Zhang, Hua,Xiao, Xue,Conte, Melissa M.,Khalil, Zeinab,Capon, Robert J.
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p. 9671 - 9676
(2013/01/16)
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- Palladium-catalyzed reduction of acid chlorides to aldehydes with hydrosilanes
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An efficient synthesis of aldehydes from acid chlorides with hydrosilanes as a reducing agent in the presence of a palladium catalyst has been achieved. A simple mixture of commercially available Pd(dba)2 and Mes 3P as a catalyst realized the reduction of various acid chlorides including aliphatic acid chlorides and a, P-unsaturated acid chlorides to the corresponding aldehydes in good to high yields under mild reaction conditions. Georg Thieme Verlag Stuttgart ? New York.
- Fujihara, Tetsuaki,Cong, Cong,Iwai, Tomohiro,Terao, Jun,Tsuji, Yasushi
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supporting information
p. 2389 - 2392
(2013/07/19)
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- Demonstration of a convergent approach to UV-polymerizable lipids bisDenPC and bisSorbPC
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Lipids containing UV-polymerizable diene moieties, such as BisDenPC 1 and BisSorbPC 2, have been extremely useful for the construction of micelles and lipid bilayers. The published syntheses have yielded lipids with only a trimethylamine head group. We have improved the syntheses of these monomers by a convergent method employing the Chabrier reaction of trimethylamine with a cyclic phospholane. This method can be extended to a variety of dialkylamine derivatives.
- Jones, Ian W.,Hall Jr.
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scheme or table
p. 3699 - 3701
(2011/08/06)
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- Rapid total syntheses utilizing "supersilyl" chemistry
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In short order: The shortest total syntheses of natural product EBC-23 (see scheme, PMB=para-methoxybenzyl, TMS=trimethylsilyl) and a polymethoxy-1-alkene to date have been accomplished in just ten total steps each from commercially available chemicals. The syntheses took advantage of highly diastereoselective supersilyl-directed cascade polyaldol reactions. Copyright
- Albert, Brian J.,Yamaoka, Yousuke,Yamamoto, Hisashi
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supporting information; experimental part
p. 2610 - 2612
(2011/05/03)
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- Comprehensive screening of octopus amphiphiles as DNA activators in lipid bilayers: Implications on transport, sensing and cellular uptake
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Dynamic octopus amphiphiles contain one charged "head," here a guanidinium cation, together several hydrophobic "tails" (or "tentacles") that can be attached and exchanged in situ by reversible hydrazone formation. Quite surprisingly, their ability to activate DNA as transporters in lipid bilayer membranes was found to increase with the number of tails (up to four) as well as with their length (up to eight carbons). Both encouraged and puzzled by these results, we decided that a comprehensive screening of octopus amphiphiles with regard to number (from one to six) and length (from three to eighteen carbons) of their tails would be appropriate at this point. For this purpose, we here report the synthesis of cationic hexahydrazide peptide dendrons together with that of aldehydes with long, saturated, unsaturated and branched hydrophobic tails. Comprehensive screening of the completed collection of tails and heads reveals that the ability of octopus amphiphiles to activate DNA transporters shifts with increasing number of tails to decreasing length of the tails. Moreover, cis-alkenyl and branched alkyl tails are more active than their linear analogs, branched aromatic tails are best. These overall very meaningful trends for octopus amphiphiles will be of importance for sensing applications and fragrant cellular uptake.
- Montenegro, Javier,Fin, Andrea,Matile, Stefan
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supporting information; experimental part
p. 2641 - 2647
(2011/05/15)
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- Modulation of the activity of histone acetyltransferases by long chain alkylidenemalonates (LoCAMs)
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A novel class of KAT modulators (long chain alkylidenemalonates, LoCAMs) has been identified. Variations of the alkyl chain length can change the activity profile from inhibition of both KAT3A/KAT2B (as derivative 2a) to the peculiar profile of pentadecylidenemalonate 1b, the first activator/inhibitor of histone acetyltransferases. Together with the powerful apoptotic effect (particularly notable if considering that anacardic acid and other KAT inhibitors are not cell permeable) appoint them as valuable biological tools to understand the mechanisms of lysine acetyltransferases.
- Milite, Ciro,Castellano, Sabrina,Benedetti, Rosaria,Tosco, Alessandra,Ciliberti, Carmen,Vicidomini, Caterina,Boully, Ludovic,Franci, Gianluigi,Altucci, Lucia,Mai, Antonello,Sbardella, Gianluca
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experimental part
p. 3690 - 3701
(2011/08/03)
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- Total synthesis of (+)-aculeatin D and (+)-6-epi-aculeatin D
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The stereoselective total synthesis of spiroketal natural product (+)-aculeatin D and unnatural (+)-6-epi-aculeatin D has been accomplished. Sharpless kinetic resolution of secondary allylic alcohol and phenyliodine(III) bis(trifluoroacetate) (PIFA)-mediated oxidative spirocyclization were used as key steps in this synthesis. Georg Thieme Verlag Stuttgart.
- Yadav,Raghavendra Rao,Ravindar,Subba Reddy
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scheme or table
p. 51 - 54
(2010/07/10)
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- Structure-Activity relationship of aliphatic compounds for nematicidal activity against pine wood nematode (Bursaphelenchus xylophilus)
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Nematicidal activity of aliphatic compounds was tested to determine a structure-activity relationship. There was a significant difference in nematicidal activity among functional groups. In a test with alkanols and 2E-alkenols, compounds with C8-C11 chain length showed 100% nematicidal activity against pine wood nematode, Bursaphelenchus xylophilus, at 0.5 mg/mL concentration. C6-C10 2E-alkenals exhibited >95% nematicidal activity, but the other compounds with C 11-C14 chain length showed weak activity. Nematicidal activity of alkyl acetates with C7-C11 chain length was strong. Compounds belonging to hydrocarbons, alkanals, and alkanoic acetates showed weak activity at 0.5 mg/mL concentration. Nematicidal activity of active compounds was determined at lower concentrations. At 0.25 mg/mL concentration, whole compounds except C8 alkanol, C8 2E-alkenol, and C7 alkanoic acid showed >80% nematicidal activity. C 9-C11 alkanols, C10-C11 2E-alkenols, C8-C9 2E-alkenals, and C9-C10 alkanoic acids showed >80% nematicidal activity at 0.125 mg/mL concentration. Only C11 alkanol exhibited strong nematicidal activity at 0.0625 mg/mL concentration, the lowest concentration that was tested. 2010 American Chemical Society.
- Seo, Seon-M.I.,Junheon, Kim,Eunae, Kim,Park, Hye-M.I.,Kim, Young-Joon,Park, I.L.-Kwon
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scheme or table
p. 1823 - 1827
(2010/09/09)
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- Identification of long chain alkylidenemalonates as novel small molecule modulators of histone acetyltransferases
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Pentadecylidenemalonate 1b, a simplified analogue of anacardic acid, was identified as the first mixed activator/inhibitor of histone acetyltransferases (HATs). It potentiates PCAF HAT activity while inhibiting those of p300/CBP and recombinant CBP. The remarkable apoptotic effect together with the ability to selectively acetylate histone versus non-histone substrates appoint 1b as a lead for the development of anticancer drugs.
- Sbardella, Gianluca,Castellano, Sabrina,Vicidomini, Caterina,Rotili, Dante,Nebbioso, Angela,Miceli, Marco,Altucci, Lucia,Mai, Antonello
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p. 2788 - 2792
(2008/12/23)
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- Synthesis and conformational analysis of stevastelin C3 analogues and their activity against the dual-specific vaccina H1-related phosphatase
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The biological activity of macrocyclic natural products depends on their conformational properties. For both the elucidation of enzyme binding affinities as well as the development of selective drugs, rigid macrocyclic scaffolds carry high potential. In this study, 13-membered cyclodepsipeptides based on the structure of naturally occurring stevastelins were studied in detail. Six diastereomeric stevastelin C3 analogues and four phosphorylated derivatives were synthesized. The synthesis of linear precursors was achieved on solid support by starting from stereoisomerically pure 2-methyl-3-hydroxy acids. Subsequent macro-lactamization gave the cyclic depsipeptides in very good yields (36-62%). The conformational space of these stevastelin C3 analogues was computationally investigated. On the basis of NMR spectroscopic data, homogeneous conformations were determined for each benzylated depsipeptide and the influence of phosphorylation on the overall conformation was investigated. Importantly, phosphorylation was found to significantly weaken the conformational preferences of the 13-membered depsipeptides. Finally, the cyclic depsipeptides were tested for activity against phosphatases. Inhibitory activity on vaccina H1-related phosphatase was observed depending on the derivatization of the cycles. The activity profiles are discussed in the light of the structural data.
- Bisek, Nicola,Wetzel, Stefan,Arndt, Hans-Dieter,Waldmann, Herbert
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supporting information; experimental part
p. 8847 - 8860
(2009/10/23)
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- Asymmetric synthesis of (+)-tetrahydropseudodistomin
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An efficient asymmetric synthesis of (+)-tetrahydropseudodistomin is described. The important synthetic features include a Maruoka asymmetric allylation and a Sharpless asymmetric dihydroxylation as key steps for the generation of chirality at C-2, -4, and -5 of the trisubstituted piperidine ring.
- Chandrasekhar,Shameem Sultana,Kiranmai,Narsihmulu
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p. 2373 - 2375
(2007/10/03)
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- Diastereodivergent strategies for the synthesis of homochiral aculeatins
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(Chemical Equation Presented) We report concise and stereocontrolled syntheses of aculeatins (-)-A, (+)-B, (+)-D, and (+)-6-epi-D. Diastereodivergent 1,3-inductions in Mukaiyama aldol coupling contribute to reduce steps and to increase flexibility with reactants having sterically restricted proximal substituents (i.e., CH2), involving either a good anti or a moderate syn 1,3-induction, depending on the nature of protecting group (P). In addition, the 3,5-syn-diol-ketone resulting from concomitant deprotection of the β-alkoxy (Tr = trityl) group proves to be remarkably stable whereas the 3,5-anti diastereoisomer cyclizes spontaneously to the corresponding tetrahydropyran hemiketal, thus enabling a useful and facile separation. The second part of our study is devoted to improving the yield and the diastereoselectivity of the final phenolic oxidation reaction leading to aculeatins.
- Peuchmaur, Marine,Wong, Yung-Sing
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p. 5374 - 5379
(2008/02/09)
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- An efficient conversion of carboxylic acids to one-carbon degraded aldehydes via 2-hydroperoxy acids
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After the formation of dianions of a carboxylic acid with lithium diisopropylamide, oxygen was bubbled into the solution to produce 2-hydroperoxy acid. Then the reaction mixture was acidified with a 2N HCl solution and subsequently elevated to 50°C to afford the aldehyde with the loss of one carbon atom. Even saturated (C10-C20) and unsaturated (C18:1) carboxylic acids were converted into the odd aldehydes (C9-C19, C17:1) in high yields. This conversion was found to be an efficient method for the preparation of carboxylic acids (Cn) to one-carbon degraded aldehydes (Cn-1) via 2-hydroperoxy acids.
- Akakabe, Yoshihiko,Nyuugaku, Takeshi
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p. 1370 - 1371
(2008/02/07)
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- Synthesis of 1-deoxysphingosine derivatives with conformationally restricted pyrrolidinediol head groups
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A family of cyclic 1-deoxysphingolipid derivatives of structure 4 has been designed and synthesized, which may serve as tumorigenesis suppressors for various cancers. Compound 4 is a second-generation analogue developed from sphingosine (1), in which a hydroxyl substituent is moved from C1 to C5 and a methylene is added for conformational rigidity between the C2-nitrogen substituent and C4. The synthetic chemistry for pyrrolidine ring closure at C3-C4 features ring-closing metathesis followed by hydroboration-oxidation.
- Dougherty, Ann M.,McDonald, Frank E.,Liotta, Dennis C.,Moody, Steven J.,Pallas, David C.,Pack, Carrie D.,Merrill, Alfred H.
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p. 649 - 652
(2007/10/03)
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- Synthesis of a novel class of fatty acids-derived isoquinolines
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Two series of novel tetrahydroisoquinoline derivatives bearing at C-1 position a carbon chain derived from fatty acids were prepared employing two complementary synthetic methodologies. The Pictet-Spengler condensation was performed on myristyl, palmityl, stearyl and oleyl aldehydes, whereas the Bischler-Napieralski cyclization used pelargonic, stearic, linolenic and arachidonic acids. The ability to apply both methods allows further labeling of the final 1-substituted-1,2,3,4-tetrahydroisoquinolines for biological studies.
- Matuszewska, Iwona,Leniewski, Andrzej,Roszkowski, Piotr,Czarnocki, Zbigniew
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p. 131 - 145
(2007/10/03)
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- 1-Deoxy-5-hydroxysphingolipids as new anticancer principles: An efficient procedure for stereoselective syntheses of 2-amino-3,5-diols
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(Chemical Equation Presented) Enantioselective preparation of the linear homoallylic alcohol I allows efficient formation of the 2-amino-3,5-diol moiety present in several biologically active compounds, including 1-deoxy-5- hydroxysphingosine analogue IV, which has exhibited excellent biological activity against colon cancer. The conversion of I into IV involves a sequence of enantioselective epoxidation of the O-tert-butoxycarbonyl derivative of I, followed by regioselective and stereospecific oxacyclization of II to introduce differentiated oxygens in III.
- Wiseman, John M.,McDonald, Frank E.,Liotta, Dennis C.
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p. 3155 - 3157
(2007/10/03)
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