- Synthesis of (Z)-5-decenol and (Z)-5-decenyl acetate, components of the sex pheromones of a variety of lepidoptera
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Two simple Wittig procedures for the synthesis of (Z)-5-decenol and (Z)-5-decenyl acetate based on the monoacetylation or monobromination of 1,5-pentanediol were followed.
- Tortajada, Amparo,Mestres, Ramon,Iglesias-Arteaga, Martin A.
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Read Online
- Diiodosilane. 4. Direct reduction of ketals and acetals in the presence of unprotected carbonyls. A case of inverted chemoselectivity
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Ketals and acetals are selectively reduced by diiodosilane to iodoalkanes in preference to ketones and aldehydes. This inversion of the normal order of reactivity of the 'protected' and 'unprotected' carbonyls allows partial reduction of polycarbonyl compounds with unusual regio- and chemoselectivity. Thus, 8,8-(ethylenedioxy)octan-2-one, 7,7-(ethylenedioxy)octanal, 3,3-(ethylenedioxy)-androstan-17-one and 3,3-(ethylenedioxy)pregnane-11,20-dione are converted to the corresponding iodo compounds.
- Keinan,Sahai,Shvily
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- Synthesis of (R)-japonilure and (4R,9Z)-9-octadecen-4-olide, pheromones of the Japanese beetle and currant stem girdler
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Asymmetric total synthesis of the sex pheromones of Japanese beetle and currant stem girdler, (R)-japonilure (1) and (4R,9Z)-9-octadecen-4-olide (2), has been achieved. Copyright Taylor & Francis Group, LLC.
- Sabitha, Gowravaram,Bhaskar,Yadagiri,Yadav
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- Stereoselective synthesis of isomers of the naturally occurring 13-hydroxy-2,4,9-tetradecatrienic acid I
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The stereoselective synthesis of (S,2E,4E,9Z)-13-hydroxy-2,4,9-tetradecatrienic acid is described. Starting from (S)-methyloxirane, the carbon chain was built by means of Wittig reactions, regioselective oxidation of the resulting dialcohol, and a diastereomerization reaction.
- Huefner, Antje,Presser, Armin
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- Chemoproteomic Evaluation of the Polyacetylene Callyspongynic Acid
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Polyacetylenes are a class of alkyne-containing natural products. Although potent bioactivities and thus possible applications as chemical probes have already been reported for some polyacetylenes, insights into the biological activities or molecular mode of action are still rather limited in most cases. To overcome this limitation, we describe the application of the polyacetylene callyspongynic acid in the development of an experimental roadmap for characterizing potential protein targets of alkyne-containing natural products. To this end, we undertook the first chemical synthesis of callyspongynic acid. We then used in situ chemical proteomics methods to demonstrate extensive callyspongynic acid-mediated chemical tagging of endoplasmic reticulum-associated lipid-metabolizing and modifying enzymes. We anticipate that an elucidation of protein targets of natural products may serve as an effective guide to the development of subsequent biological assays that aim to identify chemical phenotypes and bioactivities.
- Nickel, Sabrina,Serwa, Remigiusz A.,Kaschani, Farnusch,Ninck, Sabrina,Zweerink, Susanne,Tate, Edward W.,Kaiser, Markus
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- Formation, Stability, and Reactivity of Radical Cations of 1-Bromo-n-chloroalkanes in Aqueous Solution: A Pulse Radiolysis Study
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Hydroxyl radicals are able to form solute radical cations in acidic aqueous solutions of 1-bromo-n-chloroalkanes (n=1-6).Depending on the value of n, the bromine centered radical cation stabilizes on coordination with an unoxidized bromine atom from another molecule (intermolecular) or with an unoxidized chlorine atom of the same molecule (intramolecular).With n=2, 5, and 6, only dimer radical cations (λmax=430-450 nm) are formed through intermolecular coordination whereas, with n=1, 3, and 4, radical cations are stabilized both by intra- and intermolecular coordination, forming intramolecular radical cations (λmax=380 nm) or dimer radical cations (λmax=425-440 nm) at low and high solute concentrations, respectively.Cl2.- is unable to undergo an electron transfer reaction with 1-bromo-2-chloroethane whereas SO4.- is able to react with 1-bromo-2-chloroethane with a bimolecular rate constant of 8.3 * 106 dm3 mol-1 s-1.The dimer radical cation of 1-bromo-2-chloroethane is a strong one-electron oxidant and is able to undergo electron transfer reaction with a number of molecules with high rate constant values (109 dm3 mol-1 s-1).The dimer radical cation decays by a deprotonation mechanism, and the stability constant is determined to be 147 dm3 mol-1 at 25 deg C.Quantum chemical calculations of the strength of the three-electron bond between two heteroatoms at a semiempirical level with AMI parametrization show good correlation with experimental results.Good correlation, between experimantal results and theoretical calculations, is also observed for variation of the net atomic charge over bromine, the ionization potential (IP) of the molecule, and the difficulty of oxidation of various alkyl halides.
- Maity, D. K.,Mohan, H.,Chattopadhyay, S.,Mittal, J. P.
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Read Online
- Radical Carbonyl Umpolung Arylation via Dual Nickel Catalysis
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The formation of carbon-carbon bonds lies at the heart of synthetic organic chemistry and is widely applied to construct complex drugs, polymers, and materials. Despite its importance, catalytic carbonyl arylation remains comparatively underdeveloped, due
- Huang, Huan-Ming,Bellotti, Peter,Erchinger, Johannes E.,Paulisch, Tiffany O.,Glorius, Frank
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supporting information
p. 1899 - 1909
(2022/02/01)
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- Acid-Catalyzed Intramolecular Ring-Opening Reactions of Cyclopropanated Oxabenzonorbornadienes with Carboxylic Acid Nucleophiles
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The present work demonstrates the ability of carboxylic acid tethered cyclopropanated oxabenzonorbornadienes (CPOBDs) to undergo ring-opening reactions in mild acidic conditions. The optimized reaction conditions involve the use of pTsOH in DCE at 90 °C. Two regioisomers are formed but the reactions are highly regioselective towards type 3 ring-opened products. It was observed that substitution at the C5 and aryl positions of CPOBD significantly hinders the ring-opening reactions leading to decreased yields of ring-opened products, although high regioselectivity for the Type 3 ring-opened products is still maintained. Herein, the first examples of acid-catalyzed intramolecular ring-opening reactions of CPOBD with carboxylic acid nucleophiles are reported.
- Ho, Angel,Pounder, Austin,Koh, Samuel,Macleod, Matthew P.,Carlson, Emily,Tam, William
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p. 1422 - 1430
(2021/12/02)
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- Design, synthesis and antiparasitic evaluation of click phospholipids
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A library of seventeen novel ether phospholipid analogues, containing 5-membered heterocyclic rings (1,2,3-triazolyl, isoxazolyl, 1,3,4-oxadiazolyl and 1,2,4-oxadiazolyl) in the lipid portion were designed and synthesized aiming to identify optimised miltefosine analogues. The compounds were evaluated for their in vitro antiparasitic activity against Leishmania infantum and Leishmania donovani intracellular amastigotes, against Trypanosoma brucei brucei and against different developmental stages of Trypanosoma cruzi. The nature of the substituents of the heterocyclic ring (tail) and the oligomethylene spacer between the head group and the heterocyclic ring was found to affect the activity and toxicity of these compounds leading to a significantly improved understanding of their structure–activity relationships. The early ADMET profile of the new derivatives did not reveal major liabilities for the potent compounds. The 1,2,3-triazole derivative 27 substituted by a decyl tail, an undecyl spacer and a choline head group exhibited broad spectrum antiparasitic activity. It possessed low micromolar activity against the intracellular amastigotes of two L. infantum strains and T. cruzi Y strain epimastigotes, intracellular amastigotes and trypomastigotes, while its cytotoxicity concentration (CC50) against THP-1 macrophages ranged between 50 and 100 μM. Altogether, our work paves the way for the development of improved ether phospholipid derivatives to control neglected tropical diseases.
- Afroudakis, Pantelis,Barrias, Emile,Bifeld, Eugenia,Borsari, Chiara,Calogeropoulou, Theodora,Clos, Joachim,Costi, Maria Paola,Ellinger, Bernhard,Fotopoulou, Theano,Fragiadaki, Irini,Georgikopoulou, Kalliopi,Gul, Sheraz,Hachenberg, Julia,Kuzikov, Maria,Magoulas, George E.,Prousis, Kyriakos C.,Roussaki, Marina,Santarem, Nuno,Scoulica, Effie,Tejera Nevado, Paloma,da Silva, Anabela Cordeiro,de Souza, Wanderley
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- Chemical proteomic analysis of palmostatin beta-lactone analogs that affect N-Ras palmitoylation
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S-Palmitoylation is a reversible post-translational lipid modification that regulates protein trafficking and signaling. The enzymatic depalmitoylation of proteins is inhibited by the beta-lactones Palmostatin M and B, which have been found to target several serine hydrolases. In efforts to better understand the mechanism of action of Palmostatin M, we describe herein the synthesis, chemical proteomic analysis, and functional characterization of analogs of this compound. We identify Palmostatin M analogs that maintain inhibitory activity in N-Ras depalmitoylation assays while displaying complementary reactivity across the serine hydrolase class as measured by activity-based protein profiling. Active Palmostatin M analogs inhibit the recently characterized ABHD17 subfamily of depalmitoylating enzymes, while sparing other candidate depalmitoylases such as LYPLA1 and LYPLA2. These findings improve our understanding of the structure–activity relationship of Palmostatin M and refine the set of serine hydrolase targets relevant to the compound's effects on N-Ras palmitoylation dynamics.
- Cravatt, Benjamin F.,Firestone, Ari J.,Hazeen, Akram,Howell, Amy R.,Luvaga, Irungu K.,Richardson, Stewart K.,Shannon, Kevin,Suciu, Radu M.,Weerasooriya, Chulangani
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supporting information
(2021/11/09)
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- Selective Hydroboration–Oxidation of Terminal Alkenes under Flow Conditions
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An efficient flow process for the selective hydroboration and oxidation of different alkenes using 9-borabicyclo(3.3.1)nonane (9-BBN) allows facile conversion in high productivity (1.4 g h?1) of amorpha-4,11-diene to the corresponding alcohol, which is an advanced intermediate in the synthesis of the antimalarial drug artemisinin. The in situ reaction of borane and 1,5-cyclooctadiene using a simple flow generator proved to be a cost efficient solution for the generation of 9-BBN.
- Elsherbini, Mohamed,Huynh, Florence,Dunbabin, Alice,Allemann, Rudolf K.,Wirth, Thomas
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supporting information
p. 11423 - 11425
(2020/08/07)
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- Bio-inspired Total Synthesis of Twelve Securinega Alkaloids: Structural Reassignments of (+)-Virosine B and (?)-Episecurinol A
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The so-called Securinega alkaloids constitute a class of tetracyclic biologically active specialised metabolites isolated principally from subtropical plants belonging to the Phyllanthaceae family. Following a strategy based on alternative hypotheses for their biosynthesis, an easy and time-efficient divergent synthesis enabled access to twelve of those alkaloids featuring (neo)(nor)securinane skeletons. Moreover, this work permitted to reassign the absolute configurations of (+)-virosine B and (?)-episecurinol A.
- Antien, Kevin,Cossío, Fernando P.,Deffieux, Denis,Lacambra, Aitor,Massip, Stéphane,Peixoto, Philippe A.,Pouységu, Laurent,Quideau, Stéphane
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- OPEN-FLASK HYDROBORATION AND THE USE THEREOF
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The present disclosure generally relates to a process for hydroboration of an alkene or alkyne using ammonia borane (AB). In particular, the present invention relates to hydroboration of an alkene or alkyne in the presence of air or moisture, and a clean process for facile preparation of an alcohol by oxidizing the organoborane so formed with hydrogen peroxide. The products, including aminodialkylboranes, ammonia trialkylborane complexes, as well as various alcohols so prepared, are within the scope of this disclosure.
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Paragraph 0046; 0058; 0059
(2018/03/25)
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- Atrijuglans hetaohei Yang sex pheromone component
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The invention discloses an atrijuglans hetaohei Yang sex pheromone component as well as extraction, identification and synthesis methods thereof. The atrijuglans hetaohei Yang sex pheromone component is synthetized through the following steps of: extracting female sexual glands during a sexual excitation period of atrijuglans hetaohei Yang through a field rearing condition; extracting sex pheromone substances form the female sexual glands, and identifying active ingredients of the sex pheromone substance; and then performing a catalytic coupling reaction. The atrijuglans hetaohei Yang sex pheromone component is anti-5-hexadecene acetate. The sex pheromone component is dissolved in an organic solvent to prepare an induced cell which is used for monitoring, predicating and forecasting the emergence period of the atrijuglans hetaohei Yang, so that scientific reference is provided for effectively preventing and treating atrijuglans hetaohei Yang in proper time.
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Paragraph 0026; 0041; 0042
(2017/04/06)
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- Dihydroarteannuin-memantine diad compounds, and synthesis method and application thereof
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The invention discloses dihydroarteannuin-memantine diad compounds, and a synthesis method and application thereof. The structure of the compounds is disclosed as Formula I. The synthesis method comprises the following steps: reducing arteannuin to obtain dihydroarteannuin, carrying out acetalation reaction on the dihydroarteannuin and 2-bromoethanol under the catalytic action of Lewis acid, and carrying out reaction on the acetalation reaction product and memantine hydrochloride to obtain the dihydroarteannuin-memantine diad compounds. The compounds are reported for the first time, have an therapeutic effect on neurodegenerative diseases, and can be used for preparing drugs for treating neurodegenerative diseases. Compared with other prior arts, the compounds disclosed by the invention have the advantages of simple preparation technique and better curative effect than memantine.
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Paragraph 0067; 0068
(2016/10/10)
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- A kind of 9Z, 11E - tetradecenoic dienol acetate method for the synthesis of
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The invention relates to a synthesis method of prodenia litura sex pheromone main component (9Z,11E)-tetradecadienol acetate. The method comprises the following steps: by using 7-bromine-(4Z,6E)-heptadienal and 1,5-pentanediol as initial raw material, firstly reducing 7-bromine-(4Z,6E)-heptadienal as 7-bromine-(4Z,6E)-heptadienol; performing Kumada cross coupling reaction on 7-bromine-(4Z,6E)-heptadienol and ethyl magnesium bromide to obtain (4Z,6E)-nonadienol; performing chlorination through thionyl chloride to obtain (3E,5Z)-9-chlorine nonadienol; reacting (3E,5Z)-9-chlorine nonadienol with magnesium to prepare a corresponding Grignard reagent; and coupling (3E,5Z)-9-chlorine nonadienol with 2-(5-bromo pentyloxy)-tetrahydropyrane prepared by 1,5-pentanediol under the catalysis of lithium tetrachlorocuprate to obtain 2-(9Z,11E-tetradecadiallyloxy)-tetrahydropyrane, and finally reacting with acetylchloride to obtain a target product (9Z,11E)-tetradecadienol acetate. The method provided by the invention has the advantages of available and cheap raw material, simple synthesis line, moderate reaction condition, high yield and low cost, and is convenient and safe to operate.
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Paragraph 0024
(2017/02/28)
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- A non-dissociative open-flask hydroboration with ammonia borane: Ready synthesis of ammonia-trialkylboranes and aminodialkylboranes
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Under open-flask conditions, ammonia borane hydroborates olefins in refluxing tetrahydrofuran. Unlike conventional hydroboration, the Lewis base (ammonia) is not dissociated from the boron center. Terminal alkenes selectively provide ammonia-trialkylborane complexes. On the other hand, internal alkenes afford aminodialkylboranes via a metal-free hydroboration-dehydrogenation sequence. Alkaline hydrogen peroxide oxidation of the products provides the corresponding alcohols in high yields.
- Ramachandran, P. Veeraraghavan,Drolet, Michael P.,Kulkarni, Ameya S.
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supporting information
p. 11897 - 11900
(2016/10/09)
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- Visible-Light-Promoted Oxidative [4 + 2] Cycloadditions of Aryl Silyl Enol Ethers
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Visible-light-promoted oxidative [4 + 2] cycloadditions of μ,3-unsaturated silyl enol ethers have been developed to efficiently and diastereoselectively construct polycyclic skeletons under mild conditions. The diastereoselectivities were dependent on the stereoconfiguration of silyl enol ether, substitutions on the link, as well as electric properties of substitutions on aryl rings. The intermediates could be trapped by TEMPO, oxygen or methanol. Mechanistic studies indicated the reaction was initiated by one-electron oxidation of the silyl enol ether.
- Yang, Bo,Lu, Zhan
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p. 7288 - 7300
(2016/08/30)
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- Glycal approach to the synthesis of macrolide (-)-A26771B
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A convergent total synthesis of a 16-membered macrolactone natural product (-)-A26771B 1 starting from 3,4,6-tri-O-acetyl-d-glucal 7 is reported. The Ferrier rearrangement of acetylated glucal 7, cross metathesis between chiral fragments 3 and 4, Yamaguchi macrolactonization and selective oxidation of the allylic alcohol are the key features of the synthesis.
- Saidhareddy, Puli,Shaw, Arun K.
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p. 29114 - 29120
(2015/04/22)
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- Synthesis of corn rootworm pheromones from commercial diols
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A mixture of stereoisomers of the corn rootworm pheromones was synthesised via the Grignard coupling of protected bromohydrins with alkylcuprate as a key step. The synthesis of 8-methyldec-2- yl propanoate (I), the northern corn rootworm Diabrotica longicornis Say pheromone, was achieved from pentane-1,5-diol in four steps with an overall yield of 35.1 % and 10-methyltridecan-2-one (II), the southern corn rootworm Diabrotica undecimpunctata howardi Barber pheromone, was synthesised from octane-1,8-diol as commercially available starting material in five steps with an overall yield of 28.7 %.
- Nguyen, Thanh-Danh,Nguyen, Cong-Hao,Im, Chan,Dang, Chi-Hien
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p. 380 - 384
(2015/02/19)
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- Design, synthesis, and in vitro evaluation of an activity-based protein profiling (ABPP) probe targeting agmatine deiminases
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Agmatine deiminases (AgDs) belong to a family of enzymes known as guanidinium group modifying enzymes (GMEs). Many pathogenic bacteria encode an AgD that participates in the catabolism of agmatine (decarboxylated arginine). This catabolism may confer a co
- Thomson, Andrew,O'Connor, Sean,Knuckley, Bryan,Causey, Corey P.
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p. 4602 - 4608
(2014/11/27)
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- TEMPO-catalyzed aerobic oxygenation and nitrogenation of olefins via C=C double-bond cleavage
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A novel TEMPO-catalyzed aerobic oxygenation and nitrogenation of hydrocarbons via C=C double-bond cleavage has been disclosed. The reaction employs molecular oxygen as the terminal oxidant and oxygen-atom source by metal-free catalysis under mild conditions. This method can be used for the preparation of industrially and pharmaceutically important N- and O-containing motifs, directly from simple and readily available hydrocarbons.
- Wang, Teng,Jiao, Ning
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p. 11692 - 11695
(2013/09/02)
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- Synthesis of the C5-C30 fragment of cyclodidemniserinol trisulfate via I2-mediated deprotection and ring closure tandem reaction
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The marine natural product cyclodidemniserinol trisulfate displayed moderate HIV-1 integrase inhibitory activity. Its novel structure triggered our interest to synthesize it. In our total synthesis effort, the natural product was dissected into four fragments based on the rational retrosynthetic analysis. All four fragments were successfully prepared with orthogonal protection. And the assembly of fragment A and B furnished the C5-C30 key subunit by employing the I2-mediated deprotection and intramolecular ketal formation tandem reaction in the presence of NaHCO3 in MeCN. Our work provided flexible and practical approaches to synthesize and derive the 3,5,7-trisubstituted 6,8-dioxabicyclo [3.2.1] octane based analogs to search for new structure HIV-1 integrase inhibitors.
- Liu, Jian-Hua,Jin, Yi,Long, Ya-Qiu
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experimental part
p. 1267 - 1273
(2010/04/02)
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- Reduction of carboxylic acid derivatives using diphenylsilane in the presence of a Rh-PPh3 complex
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Reductions of carboxylic acid derivatives by silanes in the presence of rhodium complexes were studied. Carboxylic esters were reduced to alcohols by diphenylsilane catalyzed by [RhCl(cod)]2/4PPh3 or [RhCl(PPh3)3] at room temperature in up to 99% yields. For example, ethyl decanoate and ethyl phenylacetate were converted to decanol and 2-phenylethanol in 98 and 92% yields, respectively. Carboxylic acids were also reduced by this reducing system to the corresponding alcohols in high yields. Furthermore, N-monosubstituted amides were reduced to secondary amines in moderate to good yields. For sterically hindered amides, the yields were moderate, and imines were produced in competitive yields.
- Ohta, Tetsuo,Kamiya, Masahiro,Nobutomo, Mami,Kusui, Keisuke,Furukawa, Isao
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p. 1856 - 1861
(2007/10/03)
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- On the synthesis of pyrinodemin A. Part 1: The location of the olefin
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The elucidation of the structure of the cytotoxic marine sponge alkaloid pyrinodemin A by synthesis is described. Based on the 13C NMR spectra of three double bond positional isomers and the natural product, it is concluded the C14′-C15′ isomer
- Romeril, Stuart P.,Lee, Victor,Baldwin, Jack E.,Claridge, Timothy D.W.
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p. 1127 - 1140
(2007/10/03)
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- NOVEL FATTY ACID ANALOGOUS
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The present invention relates to novel fatty acid analogous of the general formula (I): R1—[xi—CH2]n—COOR2 wherein R1 is: a C6-C24 alkene with one or more double bonds and/or with one or more triple bonds, and/or a C6-C24 alkyne, and/or a C6-C24 alkyl substituted in one or several positions with one or more compounds selected from the group comprising fluoride, chloride, hydroxy, C1-C4 alkoxy, C1-C4 alkylthio, C2-C5 acyloxy or C1-C4 alkyl, and wherein R2 represents hydrogen or C1-C4 alkyl, and wherein n is an integer from 1 to 12, and wherein i is an odd number and indicates the position relative to COOR2, and wherein Xi independent of each other are selected from the group comprising O, S, SO, SO2, Se and CH2, and with the proviso that at least one of the Xi is not CH2, and with the proviso that if R1 is an alkye, then the carbon-carbon triple bond is positioned between the (ω-1) carbon and the (ω-2) carbon, or between the (ω-2) carbon and the (ω-3) carbon, or between the (ω-3) carbon and the (ω-4) carbon, a salt, prodrug or complex thereof, which can be used for the treatment and/or prevention of syndrome X, obesity, hypertension, fatty liver, diabetes, hyperglycaemia, hyperinsulinemia and stenosis. Further, the invention relates to a nutritional composition comprising said fatty acid analogues, and a method for reducing the total weight, or the amount of adipose tissue in an animal.
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- Combination preparation of estrogen and anti-estrogen
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The invention describes a combination preparation of an oestrogen and an antioestrogen, characterized in that the oestrogen is selected from the group consisting of 17-β-oestradiol, 17-α-ethynyloestradiol, oestriol, oestrone, oestrone sulphate, oestrogen sulphamates, 17α-oestradiol, mestranol, stilboestrol and naturally conjugated oestrogens and in that the antioestrogen is a substituted 7α-(ξ-aminoalkyl)oestratriene of the general formula I The combination preparation according to the invention can be used for hormone substitution therapy.
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- Synthesis haptens and development of an immunoassay for the olive fruit fly pheromone
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An enzyme-linked immunosorbent assay (ELISA) for the olive fruit fly pheromone, Bactrocera oleae Gmelin, was developed. The assay uses polyclonal antibodies, raised in rabbits, against (±)-β-[3-(1,7-dioxaspiro[5.5] undecane)]propionic acid, 2 (hapten I), conjugated to the KLH (keyhole limpet hemocyanin) by the carbodiimide method. A second hapten, (±)-δ-[3- (1,7-dioxaspiro[5.5]undecane)]-butylamine, 3 (hapten II), after conjugation to a biotin moiety, was used for indirect immobilization onto ELISA microwells precoated with the glycoprotein avidin. The developed ELISA method measures the synthetic olive fruit fly pheromone in concentrations ranging between 0.08 and 10 μg/mL and shows great promise for practical applications for pheromone detection in environmental and biological samples. The results obtained strongly indicate that this technique, to our knowledge the first insect pheromone enzyme-linked immunosorbent assay so far reported, is a fast, sensitive, inexpensive, and highly convenient method for the analysis of a volatile and low molecular weight compound such as 1,7-dioxaspiro[5.5]undecane, 1.
- Neokosmidi, Afroditi,Ragoussis, Valentine,Zikos, Christos,Paravatou-Petsotas, Maria,Livaniou, Evangelia,Ragoussis, Nikitas,Evangelatos, Gregory
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p. 4368 - 4374
(2007/10/03)
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- KETONES AND REDUCED KETONES AS THERAPEUTIC AGENTS FOR THE TREATMENT OF BONE CONDITIONS
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The present invention pertains to certain ketones and reduced ketones and derivatives thereof which, inter alia, inhibit osteoclast survival, formation, and/or activity; and/or inhibit bone resorption, and more particularly to compounds of the formulae: (1) (2) wherein: Ar1 is independently a biphenyl, phenanthryl, fluorenyl, or carbazolyl, and is optionally substituted; Ralk is independently a C2-10alkylene group, and is optionally substituted; -ORO, if present, is independently -OH or -ORK; -ORK, if present, is independently selected from: -O-RK1; -O-C(=O)RK2; -O-C(=O)ORK3; -O-S(=O)2ORK4; Q is independently -OH or -OROT; wherein: -OROT, if present, is independently selected from: -O-RE1; -O-C(=O)-RE2; -O-C(=O)-O-RE3; -O-C(=O)-O-SO3RE4; -O-C(=O)-O-(CH2)n-COORE5; -O-C(=O)-(CH2)n-NRN1RN2; -O-C(=O)-(CH2)n-NH-C(=O)RE6; -O-C(=O)-(CH2)n-C(=O)-NRN3RN4; -O-P(=O)(ORE7)(ORE8); -O-RPA; RPA, if present, is an organic group which incorporates a phosphonic acid group; with the proviso that if -OROT is -O-RE1, then RE1 is not a phenyl group substituted with a sulfonyl group; and pharmaceutically acceptable salts, solvates, amides, esters, ethers, chemically protected forms, or prodrugs thereof. The present invention also pertains to pharmaceutical compositions comprising such compounds, and the use of such compounds and compositions, both in vitro and in vivo, to inhibit osteoclast survival, formation, and/or activity, and to inhibit conditions mediated by osteoclasts and/or characterised by bone resorption, in the treatment of bone disorders such as osteoporosis, rheumatoid arthritis, cancer associated bone disease, Paget's disease, aseptic loosening of prosthetic implants, and the like; and/or in the treatment of conditions associated with inflammation or activation of the immune system.
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Page 74; 100
(2008/06/13)
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- Functional group transformations of diols, cyclic ethers, and lactones using aqueous hydrobromic acid and phase transfer catalyst under microwave irradiation
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Synthesis of bromoalkanols has been achieved from diols, ethers, and lactones using aq HBr (48%) and tetrabutylammonium iodide/bromide as phase transfer catalyst under microwave irradiation. This environmentally benign route provides enhanced yields of products and does away with the use of benzene as compared to existing conventional methods.
- Kad, Goverdhan L.,Kaur, Irvinder,Bhandari, Monica,Singh, Jasvinder,Kaur, Jasamrit
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p. 339 - 340
(2013/09/06)
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- 11BETA-HALOGEN-7ALPHA-SUBSTITUTED ESTRATRIENES, METOD FOR PRODUCING PHARMACEUTICAL PREPARATIONS CONTAINING SAID 11BETA-HALOGEN-7ALPHA- SUBSTITUTED ESTRATRIENES AND USE OF THE SAME FOR PRODUCING MEDICAMENTS
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This invention describes the new 11β-halogen-7α-substituted estratrienes of general formula I in which R11 is a fluorine or chlorine atom, and the other substituents have the meanings that are explained in more detail in the description. The compounds have antiestrogenic properties or tissue-selective estrogenic properties and are suitable for the production of pharmaceutical agents.
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- Synthesis of a possible structure of pyrinodemin A
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An alternative possible structure of pyrinodemin A is synthesised. The 13C NMR of the synthetic product 3 is in better agreement with the literature data.
- Romeril, Stuart P.,Lee, Victor,Claridge, Timothy D.W.,Baldwin, Jack E.
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p. 327 - 329
(2007/10/03)
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- Studies toward the total synthesis of mumbaistatin, a highly potent glucose-6-phosphate translocase inhibitor. Synthesis of a mumbaistatin analogue
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A strategy for the total synthesis of the highly potent glucose-6-phosphate translocase inhibitor mumbaistatin (1) and structural analogues was elaborated. Such compounds represent a lead structure in the development of potential new drugs for the treatment of diabetes. To evaluate the general strategy, the close mumbaistatin analogue 10 was synthesized in a convergent manner. The anthraquinone building block 20 was efficiently prepared via aryne/phthalide annulation. After conversion of 20 into the corresponding 9,10-dimethoxyanthracene-1-carbaldehyde derivative (13), coupling with a lithiated arene (12) and subsequent multiple oxidation under Jones conditions yielded the mumbaistatin analogue 10. The preparation of the functionalized arene intermediates was achieved exploiting highly regioselective bromination and ortho-lithiation reactions.
- Kaiser, Florian,Schwink, Lothar,Velder, Janna,Schmalz, Hans-Guenther
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p. 9248 - 9256
(2007/10/03)
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- Synthesis of two Unique Compounds, a Ceramide and a Cerebroside, Occurring in Human Stratum Corneum
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The cerebroside 1a and the ceramide 1b, both playing important roles in epidermal barrier function, were synthesized by N-acylation of 1-O-glucosylated C18-sphingosine 2 and C18-sphingosine 8, respectively, with O-acyl fatty acid 3. The required compound 3 was obtained from ω-hydroxy fatty acid 6 and linoleic acid 7 by esterification. The ω-hydroxy C30-fatty acid 6 was prepared as follows: Copper-catalyzed coupling of ω-hydroxy alkyl halide 11 with the Grignard reagent derived from bromo compound 13 afforded after oxidation C17-aldehyde 15. Wittig reaction with phosphonium salt 10, derived from ω-bromo-tridecanoic acid 9, and subsequent hydrogenation and O-deprotection furnished 6 in high yield.
- Mueller, Silvia,Schmidt, Richard R.
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p. 779 - 784
(2007/10/03)
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- Synthesis of cyclic ethers and allylic sulfides by rearrangement of phenylsulfanyl substituted 1,n-diols with toluene-p-sulfonic acid and with toluene-p-sulfonyl chloride
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Rearrangement of a series of l,n-diols (n = 2 to 12), with a PhS-group adjacent to one OH group, under two sets of conditions gives single compounds in excellent yield drawn for four possible classes of products. The effect of the chain length helps in the understanding of the different cyclisation modes and the mechanism of the rearrangements. The Royal Society of Chemistry 1999.
- Djakovitch, Laurent,Eames, Jason,Fox, David J.,Sansbury, Francis H.,Warren, Stuart
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p. 2771 - 2782
(2007/10/03)
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- 7α-(ξ-aminoalkyl)-estratrienes, process for their production, pharmaceutical preparations which contain these 7α-(ξ-aminoalkyl)-estratrienes as well as their use for the production of pharmaceutical agents
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This invention describes new, substituted 7α-(ξ-aminoalkyl)-estratrienes of general formula I STR1 in which side chain SK is a radical of partial formula STR2 as well as their physiologically compatible addition salts with organic and inorganic acids. The new compounds represent compounds with very strong antiestrogenic action. The compounds according to the invention are, on the one hand, pure antiestrogens, or, on the other hand, antiestrogens with estrogenic partial action. Based on this spectrum of action, the new compounds are highly suitable for the production of pharmaceutical agents for tumor therapy and hormone replacement treatment.
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- An efficient Fischer indole synthesis of avitriptan, a potent 5-HT(1D) receptor agonist
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An efficient synthesis of antimigraine drug candidate avitriptan (1, BMS 180048) is reported. The key step is a two-phase Fischer indolization reaction between hydrazine 6 and 5-chlorovaler-aldehyde, 20, to give the chloropropylindole 35, which is susceptible to acid-catalyzed degradation under the reaction conditions required for its formation. Sequential coupling of 35 with piperazine, 26, and 4-chloro-5-methoxypyrimidine, 24, gives the title compound in 40-45% overall yield. Significant improvements in the syntheses of the known starting materials, hydrazine 6, 5- chlorovaleraldehyde, 20, and 4-chloro-5-methoxypyrimidine, 24, were also achieved.
- Brodfuehrer,Chen,Sattelberg T.R.,Smith,Reddy,Stark,Quinlan,Reid
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p. 9192 - 9202
(2007/10/03)
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- Sodium bis(2-methoxyethoxy)aluminium hydride in petroleum ether; a reagent for the selective reduction of brominated fatty esters to bromo alcohols
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The combination of NaH2Al(OCH2CH2OMe)2/petroleum ether was found to be highly effective for the selective reduction of long chain esters to alcohols in the presence of alkyl bromides.
- Wells, Andy
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p. 1143 - 1147
(2007/10/03)
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- Vinylcyclobutanols: A composite functional group?
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The effect of small strained rings on chemical reactivity was probed by the examination of the behavior of vinylcyclobutanols as terminators in cyclization reactions. The substrates were readily available by the addition of vinyllithium reagents bearing acetals as cyclization initiators to cyclobutanone. Bronsted and Lewis acids both promoted cyclization in contrast to vinylcyclopropanol terminators for which Bronsted acids failed. The products are spirocycles consisting of a cyclopentanone derived from ring expansion of the cyclobutanol and the second ring derived by attack of the terminator on the initiator. Spirocyclization to [4.5] and [4.6] systems proceeded smoothly, whereas spirocyclization to a [4.7] system failed. Attaching the cyclization termini to a preexisting ring system (whereby tricycles consisting of a fused bicycle and a spirocycle are formed) expands the scope of the cyclization to include the [4.7] ring system even at 0.01 M, a rather high concentration for such an unfavorable ring system. The diastereoselectivity generally placed the initiator substituent and the carbon-carbonyl bond of the cyclopentanone ring trans on the newly formed ring. Cyclic acetals and the free aldehyde also served as initiators. The mechanistic implications of these observations are discussed.
- Trost, Barry M.,Chen, Deborah W. C.
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p. 12541 - 12554
(2007/10/03)
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- A remarkably simple process for monoprotecting diols
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Lipase from pig pancreas (PPL) has been shown to catalyse selectively the hydrolysis of alkane-1,n-diol bis-acetates into the corresponding monoacetate.
- Houille, Olivier,Schmittberger, Thierry,Uguen, Daniel
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p. 625 - 628
(2007/10/02)
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- A biomimetic approach to the manzamine alkaloids
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Results from model studies of a synthetic approach to the manzamine alkaloids based on a biogenetic theory are reported together with the synthesis of a plausible biogenetic precursor to these alkaloids.
- Baldwin, Jack E.,Claridge, Tim D. W.,Culshaw, Andrew J.,Heupel, Florian A.,Smrckova, Svatava,Whitehead, Roger C.
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p. 6919 - 6922
(2007/10/03)
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- Synthesis and conformational analysis of 2,9-disubstituted 1-oxaquinolizidines
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The synthesis of (2S,9R,10S)-9-(5-((tert-butyldiphenylsilyl)oxy)pentyl)-2-(hydroxymethy l)-1-oxaquinolizidine (29a) from (S)-malic acid, 1,5-pentanediol, and trifluoroacetamide is reported. Conformational analysis using molecular mechanics calculations an
- Borjesson,Csoregh,Welch
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p. 2989 - 2999
(2007/10/02)
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- Design and synthesis of analogues of ionomycin
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Based on the analysis of the crystal structure of the Ca2+ salt of ionomycin and the chemical and physical data on ionomycin, a number of ionomycin analogues have been synthesized to study the structural features affecting the Ca2+ binding and transport. Compounds 2, 3, and 4 were synthesized to study the effect of additional intramolecular oxygen coordination sites on Ca2+ transport. Compounds 5a-5d were prepared to study the effect of lipid solubility on Ca2+ binding and transport. Compounds 6a-6c were prepared to study the effect of the distance between the β-diketone and the carboxyl group on Ca2+ transport. A general synthetic route to these compounds has been developed. The key reactions in this route are the consecutive regioselective alkylations of the dianion of 2,4-pentanedione with the appropriate bromides.
- Hu,Weiler
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p. 1500 - 1511
(2007/10/02)
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- Studies related to fatty acids desaturation. II. Preparation of iso-linoleic and iso-vernolic acids
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New iso-vernolic and iso-linoleic acids have been prepared in order to study their potential inhibition action during in vivo desaturation of oleic acid in vegetal sources. - Keywords: Δ12-desaturase / modified fatty acids / Z,ω-octenyl bromides / iso-linoleic acids / iso-vernolic acids
- Gruiec, Regine,Noiret, Nicolas,Patin, Henri
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p. 699 - 705
(2007/10/02)
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- Synthesis of Alkylphenols and -catechols from Plectranthus albidus (Labiatae)
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In the preceding paper, we described the isolation and structure elucidation of a series of even-numbered phenol- or pyrocatechol-derived 1-arylalkane-5-ones.To establish the assigned structures unambiguously and to have larger quantities available for physiological testing, the following compounds were prepared: in the alkylphenol series, 1-(4'-hydroxyphenyl)tetradecan-5-one (2a), 1-(4'-hydroxyphenyl)hexadecan-5-one (2b), and 1-(4'-hydroxyphenyl)octadecan-5-one (2c); in the alkylcatechol series, 1-(3',4'-dihydroxyphenyl)decan-5-one (3a; not isolated as a natural compound), 1-(3',4'-dihydroxyphenyl)dodecan-5-one (3b), 1-(3',4'-dihydroxyphenyl)tetradecan-5-one (3c), 1-(3',4'-dihydroxyphenyl)hexadecan-5-one (3d), 1-(3',4'-dihydroxyphenyl)octadecan-5-one (3e), and 1-(3',4'-dihydroxyphenyl)icosan-5-one (3f); in the alkenylphenol series, (Z)-1-(4'-hydroxyphenyl)octadec-13-en-5-one (4a) and (E)-1-(4'-hydroxyphenyl)octadec-13-en-5-one (4b); in the alkenylcatechol series, (E,E)-1-(3',4'-dihydroxyphenyl)deca-1,3-dien-5-one (1) and (Z)-1-(3',4'-dihydroxyphenyl)octadec-13-en-5-one (5).All compounds proved to be identical with the previously assigned structures.Compound 1 was synthesized by regioselective aldol condensation of heptan-2-one with (E)-3-(3',4'-dimethoxyphenyl)prop-2-enal (6d; Scheme 1), the phenols 2a-c and the catechols 3a-f by addition of the corresponding alkyl Grignard reagent to 5-(4'-methoxyphenyl)- or 5-(3',4'-dimethoxyphenyl)pentanal (17c and 18c, resp.; Scheme 4), and the olefins 4a, 4b and 5 from 17c or 18c via the 9-O-silyl-protected 13-(4'-methoxyphenyl)- or 13-(3',4'-dimethoxyphenyl)tridecanals (26 and 27, resp.) and Wittig olefination as the key steps (Scheme 5).
- Buergi, Christoph,Liu, Gui,Rueedi, Peter
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p. 1901 - 1915
(2007/10/02)
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- Total synthesis of patulolide C and its homo, nor, and iso analogs
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The stereospecific total synthesis of the naturally occurring macrolide patulolide C 19Eb as well as its iso, nor, and homo analogs is described by applying the photoinduced rearrangement of enantiomerically pure epoxy diazomethyl ketones 14 to γ-hydroxy α,β-unsaturated esters 15 as the key step. The required epoxy diazomethyl ketones 14 are obtained by a Sharpless epoxidation of an appropriate allylic alcohol, followed by ruthenium tetraoxide oxidation to an oxiranecarboxylic acid, conversion into amixed anhydride, and treatment with diazomethane. Macrolide 19Zb, which is a geometrical isomer of 19Eb, turned out to be a diastereomer of natural macrolide isopatulolide C, which implies the 4R,11R configuration for this natural material. X-ray diffraction analyses of 19Ea and 19Eb show that there is a considerable difference in spatial arrangement; particularly, the different torsion angles between the carbonyl and olefinic bonds are noteworthy. The conformational behavior of these macrolides is also deduced from the NMR and UV spectra.
- Leemhuis,Thijs,Zwanenburg
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p. 7170 - 7179
(2007/10/02)
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- Anti-androgenic cyclo and bicyclo alkenes
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Compounds having the formula (i), (ii) and (iii), STR1 where R is H, alkyl of 1 to 6 carbons, or CO--R 2 where R 2 is alkyl of 1 to 6 carbons; R 1 is H, CH 3, or (CH 2) m --CH 3 ; n is an integer having the values of 2 to 10, m is an integer having the values of 1 to 6, have anti-androgen activity on secondary androgen receptor sites. The compounds are useful for treating mammals, including humans afflicted with acne, male pattern baldness, adhesions and keloids. The compounds are also effective for treating other diseases or conditions which are related to androgen receptors, such as undesirable formation of breast capsules in females after breast augmentation surgery, osteoarthritis and symptoms of Alzheimer''s disease. The compounds also have inhibitory effect on the metabolism of certain microorganisms and fungi of the kind, the metabolism of which is normally known to be controllable by anti-androgen compounds.
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- Synthesis of a 11-deoxyprostanoid in the area of Preclavulones: (±)- 8,12-trans-(5Z-14Z)-9-oxo-prosta-5,14-dienoic acid from 2-allyl-2- cyclopenten-1-one
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Following our research on the arachidonic acid metabolites and their derivatives with potential biological activity, we describe the synthesis of the (±-8,12-trans-(5Z, 14Z)-9-oxo-prosta-5,14-dienoic acid, a 11- deoxyprostanoid correlated to the class of Preclavulones, one of the unusual families of marine eicosanoids from the coral Clavularia Viridis with considerable biological interest.
- Di Giacomo,Leggeri,Papeo,Pirillo,Traverso
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p. 379 - 385
(2007/10/02)
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- Pheromone Evaluation of Four Geometric Isomers of 4,11-Hexadecadienal toward Male Eri-Silk Moths
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Four geometric isomers of 4,11-hexadecadienal were prepared and their pheromone activities to male eri-silk moths were evaluated by using the fluttering test and electro-antennography.None of these compounds showed any activity in spite of their similar structure to other pheromone mimics and to the natural pheromone.These results suggest that the presence of 6,11-double bonds is essential for pheromone activity.
- Tomida, Ichiro,Mayesawa, Tsuneaki
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p. 1962 - 1965
(2007/10/02)
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- Pheromones: 87. An efficient synthesis of (6E,11Z)-6,11-hexadecadienyl acetate and (6E,11Z)-6,11-hexadecadienal: Female sex pheromone components of Antheraea pernyi and A. polyphemus (Lepidoptera: Saturniidae)
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(6E,11Z)-Hexadecadienyl acetate (15) and the corresponding aldehyde 16, the female sex pheromone components of Antheraea pernyi and A. polyphemus (Lepidoptera; Saturniidae) have been synthesized in 32% and 27% overall yields, respectively, and in 99% isomeric purity. Tetrahydropyran (1) was used as the starting material to obtain 5-bromopentanol (3) which was subsequently chain elongated to 7-(tetrahydropyran-2-yloxy)-1-heptyne (5) by the standard procedures. The organolithium compound from 5 was coupled with (Z)-1-bromo-4-nonene (11), obtained from the Wittig reaction between pentyltriphenylphosphonium bromide (9) and 4-(tetrahydropyran-2-yloxy)butanal (8) followed by bromination. The product, (Z)-1-(tetrahydropyran-2-yloxy)-11-hexadecen-6-yne (12) which resulted, was reduced with sodium/liquid ammonia to give 13 with the E-6 bond. Removal of the protecting group resulted in the desired alcohol 14 which on acetylation and oxidation gave the desired acetate 15 and the aldehyde 16, respectively.
- Bestmann,Gunawardena
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p. 1239 - 1241
(2007/10/02)
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