cas 62992-46-5, 2-(4-PENTYNYLOXY)TETRAHYDRO-2H-PYRAN 9&

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Bedoukian
p. 1111,1112
(1971)
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Syntheses and stereochemical assignment of toxic C17-polyacetylenic alcohols, virols A, B, and C, isolated from water hemlock (Cicuta virosa)
In the course of our study on neurotoxic C17-polyacetylenic alcohols of the toxic plant, Cicuta virosa, virols A (1), B (2), and C (3) were synthesized by stereoselective routes to confirm their stereochemistry and to obtain supply of these compounds for pharmacological study. The syntheses used chiral 3-hydroxy-1-alkyne building blocks, Pd(0)CuI(I)-catalyzed coupling of acetylene with vinyl chloride, and heterocoupling reaction of acetylene mediated by CuI. As a result, the absolute configuration of the stereogenic center of virols A (1), B (2), and C (3) was confirmed as S, S, and S, respectively.
Uwai, Koji,Oshima, Yoshiteru,Sugihara, Takumichi,Ohta, Tomihisa
p. 9469 - 9480
(1999)
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Total synthesis of the antimicrobial fatty acid (5Z,9Z)-14-methylpentadeca-5,9-dienoic acid and its longer-chain analog (5Z,9Z)-24-methylpentacosa-5,9-dienoic acid
The antimicrobial marine fatty acid (5Z,9Z)-14-methylpentadeca-5,9-dienoic acid, recently identified in the phospholipids of the Caribbean gorgonian Eunicea succinea, and its longer-chain analog (5Z,9Z)-24-methylpentacosa-5,9-dienoic acid, initially identified in the phospholipids of the sponge Petrosia ficiformis, have been synthesized for the first time through a common synthetic route. A combination of alkyne-bromide coupling and Wittig reaction resulted in the best combination for assembling the Δ5,9 functionality in high yield and stereoselectivity.
Reyes, Elba D.,Carballeira, Nestor M.
p. 1195 - 1198
(1997)
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Use of Imidazo[1,5-a]pyridin-3-ylidene as a Platform for Metal-Imidazole Cooperative Catalysis: Silver-Catalyzed Cyclization of Alkyne-Tethered Carboxylic Acids
Silver complexes with 5-(4-(tert-butyl)-1H-imidazol-1-yl)-imidazo[1,5-a]pyridin-3-ylidene ligands were synthesized as metal-imidazole acid-base cooperative catalysts. Single crystal XRD analysis revealed that the silver atom was located in the vicinity of
Rawat, Vishal Kumar,Higashida, Kosuke,Sawamura, Masaya
supporting information
p. 1631 - 1637
(2021/02/03)

Stereospecific synthesis of (4e,10z)-4,10-tetradecadienyl acetate, the major sex pheromone of apple leaf miner moth, phyllonorycter ringoniella
The main component of the sex pheromone of many lepidopteran pests, (4E,10Z)-4,10-tetradecadienyl acetate (1) has been synthesized stereoselectively by using a simple route with 4-pentynol as a starting material. The stereoselective formation of the 4E double bond is based on the stereospecific reduction of internal alkyne with lithium aluminium hydride (LAH) while Wittig reaction was used to achieve 10Z double bond in the target pheromone component. The GC purity of the final acetate was achieved 97.87% while isomeric purities are more than 99%. The green chemistry principle shows a new concept towards the multistep pheromone synthesis via green metrics calculations.
Awalekar, Ramchandra,Jagadhane, Kishor,Usmani, Shams,Salunkhe, Shilpa,Jamale, Dattatray,Hangirgekar, Shankar,Kolekar, Govind,Anbhule, Prashant
p. 588 - 593
(2021/09/30)

Synthesis method of caproic acid-D7
The invention provides a synthesis method of caproic acid-D7, which comprises the following steps of: 1) under the protection of N2, preparing a compound 2 from a compound 1 and DHP in the presence ofdextral camphorsulfonic acid, 2) performing substitution reaction on the compound 2 and deuterated methyl iodide in the presence of n-butyllithium to obtain a compound 3, 3) under the protection of N2, dissolving the compound 3 in methanol, and in the presence of p-toluenesulfonic acid monohydrate, preparing a compound 4, 4) carrying out reduction reaction on the compound 4 in methanol in the presence of 10wt% palladium on carbon and in a deuterium atmosphere to obtain a compound 5, and 5) carrying out oxidation reaction on the compound 5, TEMPO and Aliquat 336 in the presence of potassium bromide and sodium hypochlorite to prepare a compound 6, namely caproic acid-D7. According to the synthesis method disclosed by the invention, highly toxic products such as potassium cyanide are prevented from being used, and the reaction operation is relatively simple and controllable.
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Paragraph 0051-0054

(2020/06/09)

Site-Selective trans-Hydrostannation of 1,3- and 1,n-Diynes: Application to the Total Synthesis of Typhonosides E and F, and a Fluorinated Cerebroside Analogue
Propargyl alcohols are privileged substrates for stereochemically unorthodox trans-hydrostannation reactions catalyzed by [Cp*RuCl]4 (Cp=pentamethylcyclopentadienyl), because an incipient hydrogen bond between the -OH group and the polarized [Ru-Cl] unit assists substrate binding. For this very reason, it is also possible to subject diyne derivatives carrying one -OH group to site-selective stannylation, even if the acetylene units are conjugated and hence, electronically coupled. An unusual temperature dependence was observed in that heating tends to improve site-selectivity, whereas per-stannylation is favored when the reaction is carried out in the cold. This counterintuitive trend can be rationalized based on spectroscopic data; additional support comes from the isolation of the unusual bimetallic complex 11. The bridging fulvene and enynyl ligands in 11 are thought to reflect an interligand redox isomerization process likely triggered by synchronous activation of the 1,3-diyne substrate by two metal centers. The preparative relevance of site-selective trans-hydrostannation is illustrated by the total synthesis of two members of the typhonoside series of glycolipids, which are endowed with neuroprotective properties. Moreover, the preparation of a fluoroalkene sphingosine analogue shows that the tin residue also serves as a versatile handle for late-stage modification of a bioactive target compound.
Mo, Xiaobin,Letort, Aurélien,Ro?ca, Drago?-Adrian,Higashida, Kosuke,Fürstner, Alois
supporting information
p. 9667 - 9674
(2018/07/14)

Synthesis method for conopomorpha sinensis bradley sex pheromone compound
The invention discloses a synthesis method for a conopomorpha sinensis bradley sex pheromone compound. The synthesis method comprises the following steps: taking 4-pentyne-1-alcohol as a starting rawmaterial, protecting hydroxyl with 3,4-dihydropyran to obtain a compound 5 protected by THP on the hydroxyl, enabling the compound 5 to generate coupled reaction with trans-dichloroethylene under co-catalysis of a metal palladium compound and cuprous iodide to obtain a compound 6; under catalysis of a metal iron compound, enabling the compound 6 to generate further coupled reaction with bromo cis-3-nonene Grignard reagent to obtain a compound 7; removing a THP protective group of the compound 7 under catalysis of toluenesulfonic acid monohydrate to form a compound 8; reducing the compound 8 toprepare (4E,6E,10Z)-hexadecatriene alcohol, and enabling the (4E,6E,10Z)-hexadecatriene alcohol to generate esterification reaction to obtain (4E,6E,10Z)-hexadecatriene acetate. The synthesis raw materials are simple and easily available, are low in cost, and the synthesis steps are short; and meanwhile, stereoselectivity is high, the yield is obviously increased, and the post-treatment is simpleand convenient.
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Paragraph 0025; 0031; 0047; 0061

(2018/12/14)

Structural diversification of the aminobicyclo[4.3.0]nonane skeleton using alkynylsilyl-derived allylic trichloroacetimidates
The amino substituted bicyclo[4.3.0]nonane is a molecular scaffold found in a wide range of natural products and medicinal agents. Despite this, synthetic methods for the general preparation of this structural motif are sparse. Here we evaluate a diastere
Mostafa, Mohamed A. B.,McMillan, Angus E.,Sutherland, Andrew
p. 3035 - 3045
(2017/04/11)

METHOD FOR PRODUCING EUSHEARILIDES
Provided are: eushearilides; a method for producing eushearilides; a production intermediate; and a pharmaceutical composition containing eushearilides. By having the Wittig reaction process, Mukaiyama Aldol reaction process and Macrolactonizaion process serve as key processes, eushearilides represented by formula (I) are efficiently produced.
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Paragraph 0064; 0065; 0066

(2017/09/12)

A Gold(I)-Catalyzed Oxidative Rearrangement of Heterocycle-Derived 1,3-Enynes Provides an Efficient and Selective Route to Divinyl Ketones
The gold-catalyzed oxidation of N-tosyl-protected 6-alkynyl-3,4-dihydro-2H-pyridines was studied in detail to obtain divinyl ketones in which one of the double bonds is embedded in a heterocyclic framework. The best reaction conditions were then extended
Nejrotti, Stefano,Prina Cerai, Gabriele,Oppedisano, Alberto,Maranzana, Andrea,Occhiato, Ernesto G.,Scarpi, Dina,Deagostino, Annamaria,Prandi, Cristina
supporting information
p. 6228 - 6238
(2017/11/15)

C-F bond cleavage enabled redox-neutral [4+1] annulation via C-H bond activation
Using α,α-difluoromethylene alkyne as a nontraditional one-carbon reaction partner, a synthetically novel method for the construction of isoindolin-1-one derivatives via Rh(III)-catalyzed [4+1] annulation reaction is reported. The 2-fold C-F bond cleavage not only enables the generation of desired product under an overall oxidant-free condition but also results in a net migration of carbon-carbon triple bond. In addition, the present reaction protocol exhibits a tolerance of a wide spectrum of functional groups due to the mild reaction conditions employed.
Wang, Cheng-Qiang,Ye, Lu,Feng, Chao,Loh, Teck-Peng
supporting information
p. 1762 - 1765
(2017/02/15)

Method for preparing spring-cankerworm sex pheromones
The invention relates to a method for preparing spring-cankerworm sex pheromones. The method includes the steps that alkynol serves as a raw material; hydroxyl is protected by dihydropyran ether; alkynyl and halogenated hydrocarbon are coupled; an acetylation reaction is carried out to generate a compound cis-4-tetradecenyl acetate and a compound cis-6-tetradecenyl acetate, wherein the total yield of the compound cis-4-tetradecenyl acetate and the total yield of the compound cis-6-tetradecenyl acetate are 58.1% and 55.2% respectively. The method has the advantages that the raw material is easy to obtain, the method is simple, the condition is mild, the total yield is high, cost is low, and the method is suitable for large-scale production. The method provides the necessary condition for replacing fruit-pest chemical-pesticide control with the wide application of the spring-cankerworm sex pheromones, and has the high theoretical significance and the quite good application value.
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Paragraph 0017; 0018; 0019; 0020

(2016/10/17)

PROCESS FOR THE PREPARATION OF TREPROSTINIL
The invention provides a new process for the preparation of treprostinil of formula (I) and its salts using several new intermediates during the building of the ringsystem.
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Page/Page column 61; 62

(2016/05/02)

STABILIZED POLYPEPTIDES AND USES THEREOF
The present invention provides inventive stabilized STAT polypeptides, pharmaceutical compositions thereof, and methods of making and using inventive stabilized STAT polypeptides.
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Sheet 20/22

(2015/04/22)

Total synthesis of (3R,16E,20E,23R)-(-)-eushearilide and structural determination of naturally occurring eushearilide
An asymmetric total synthesis of the proposed structure of (16Z,20E)-eushearilide, a novel 24-membered macrolide, was achieved via an enantioselective aldol reaction and 2-methyl-6-nitrobenzoic anhydride-mediated macrolactonization. The obtained synthetic compounds were not identical to the natural product. The newly proposed most likely structure of eushearilide, (±)-(16E,20E)-eushearilide, was determined on the basis of detailed NMR analysis, and (3R,16E,20E,23R)-(-)-eushearilide was successfully synthesized. A comparison of the optical rotation of (3R,16E,20E,23R)-(-)-eushearilide with that of the natural product confirmed that the true structure of naturally occurring eushearilide is the (3S,16E,20E,23S)-(+)-form.
Tonoi, Takayuki,Kawahara, Ryo,Yoshinaga, Yutaka,Inohana, Takehiko,Fujimori, Keiko,Shiina, Isamu
supporting information
p. 1356 - 1359
(2015/03/04)

Oxygenated Metabolites of n-3 polyunsaturated fatty acids as potential oxidative stress biomarkers: Total synthesis of 8-F3t-IsoP, 10-F 4t-NeuroP and [D4]-10-F4t-NeuroP
A wide variety of metabolic products of polyunsaturated fatty acids is of paramount importance for improving our medical knowledge in the field of oxidized lipids. Two novel metabolites of n-3 polyunsaturated fatty acids, 8-F3t-IsoP and 10-F4t-NeuroP as well as a deuterated derivative thereof were synthesized based on an acetylenic intermediate. An original approach achieved lateral chain insertion of 8-F3t-IsoP by a ring-closing alkyne metathesis/semi-reduction strategy together with a temporary tether. Three for the price of one! Two strategies, Caruso coupling or ring-closing alkyne metathesis (RCAM), enabled the synthesis of 8-F 3t-IsoP and 10-F4t-NeuroP and its deuterated derivative from acetylenic intermediateA (see scheme). Such compounds represent potential biomarkers of neuronal oxidative stress.
Guy, Alexandre,Oger, Camille,Heppekausen, Johannes,Signorini, Cinzia,Defelice, Claudio,Fuerstner, Alois,Durand, Thierry,Galano, Jean-Marie
supporting information
p. 6374 - 6380
(2014/06/09)

Intramolecular nitrone dipolar cycloadditions: Control of regioselectivity and synthesis of naturally-occurring spirocyclic alkaloids
The intramolecular nitrone dipolar cycloaddition of in situ-generated nitrones such as compound 26 has been used for the synthesis of cyclic isoxazolidines 27 and 29. The regioselectivity of the intramolecular cycloaddition depends on the nature of the terminal substituent on the dipolarophile. The influence of the substituent on the regioselectivity of the cycloaddition has been examined using several model systems and two methods of nitrone formation. These studies demonstrated that the cyano-substituent plays a special role in favouring the formation of the 6,6,5-ring fused adduct 27 under thermodynamically controlled conditions. The utility of the cyclo-adduct 57 (see Scheme 12) as a precursor for the naturally occurring histrionicotoxins is illustrated by the synthesis of three "unsymmetrical" (i.e. with each side chain bearing different functional groups) members of the histrionicotoxin family HTX-259A, HTX-285C and HTX-285E (2, 3 and 4 respectively).
Hodges, Alastair J.,Bond, Andrew D.,Holmes, Andrew B.,Roughley, Stephen D.,Smith, Catherine J.,Adams, Joseph P.,Ryan, John H.,Saubern, Simon,Newton, Annabella F.,Press, Neil J.,Turnbull, Michael D.
supporting information
p. 8963 - 8974,12
(2012/12/12)

Intramolecular nitrone dipolar cycloadditions: Control of regioselectivity and synthesis of naturally-occurring spirocyclic alkaloids
The intramolecular nitrone dipolar cycloaddition of in situ-generated nitrones such as compound 26 has been used for the synthesis of cyclic isoxazolidines 27 and 29. The regioselectivity of the intramolecular cycloaddition depends on the nature of the terminal substituent on the dipolarophile. The influence of the substituent on the regioselectivity of the cycloaddition has been examined using several model systems and two methods of nitrone formation. These studies demonstrated that the cyano-substituent plays a special role in favouring the formation of the 6,6,5-ring fused adduct 27 under thermodynamically controlled conditions. The utility of the cyclo-adduct 57 (see Scheme 12) as a precursor for the naturally occurring histrionicotoxins is illustrated by the synthesis of three "unsymmetrical" (i.e. with each side chain bearing different functional groups) members of the histrionicotoxin family HTX-259A, HTX-285C and HTX-285E (2, 3 and 4 respectively).
Hodges, Alastair J.,Adams, Joseph P.,Bond, Andrew D.,Holmes, Andrew B.,Press, Neil J.,Roughley, Stephen D.,Ryan, John H.,Saubern, Simon,Smith, Catherine J.,Turnbull, Michael D.,Newton, Annabella F.
supporting information
p. 8963 - 8974
(2013/01/15)

(Z)-N-(4-Decenoyl)homoserine lactone, a new quorum-sensing molecule, produced by endobacteria associated with Mortierella alpina A-178
N-Acylhomoserine lactones (AHLs) are the conserved quorum-sensing signal molecules in Gram-negative bacteria. (Z)-N-(4-Decenoyl)homoserine lactone (1), a new AHL, was isolated from the culture broth of the fungus Mortierella alpina A-178 harboring bacterial endosymbionts, called endobacteria. The structure and absolute configuration of 1 were elucidated by EI-MS, chemical synthesis, and chiral GC analysis. The compound induced the expression of a QS-regulated reporter gene in Agrobacterium tumefaciens NTL4, although its activity was lower than that of N-decanoylhomoserine lactone (6).
Kai, Kenji,Kasamatsu, Koji,Hayashi, Hideo
p. 5441 - 5444
(2012/10/30)

The intramolecular allenolate rauhut-currier reaction
An intramolecular Rauhut-Currier reaction utilizing alkynoates as the initial conjugate acceptor affords densely functionalized 5- and 6-membered rings from ynoate-enoate, ynoate-enenitrile, and alkynyl sulfone-enenitrile substrates. Trialkylphosphines ca
MacKay, James A.,Landis, Zachary C.,Motika, Stephen E.,Kench, Margaret H.
p. 7768 - 7774
(2012/11/06)

TRICYCLIC SULFONAMIDE COMPOUNDS AND METHODS OF MAKING AND USING SAME
The invention provides tricyclic sulfonamide compounds and their use in treating medical disorders, such as obesity. Pharmaceutical compositions and methods of making various tricyclic compounds are provided. The compounds are contemplated to have activity against methionyl aminopeptidase 2.
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Page/Page column 75

(2012/12/13)

Synthesis of 3,4-dimethylidene oxacycles through Prins-type cyclization of allenylmethylsilanes
An efficient synthesis of 3,4-dimethylidene oxacycles including oxolanes and oxepanes through Prins-type cyclization of hydroxy(allenylmethyl)silanes is described. We have shown that 2-substituted tetrahydrofuran derivatives could be produced by using thi
Ullapu, Punna Reddy,Kim, Young Seub,Lee, Jae Kyun,Pae, Ae Nim,Kim, Youseung,Min, Sun-Joon,Cho, Yong Seo
supporting information; scheme or table
p. 2092 - 2100
(2011/10/31)

Discovery of orally available 8-aza-5-thiaProstaglandin E1 analogs as highly selective EP4 agonists
Analogs 8-aza-16-aryl prostaglandin E1 (PGE1) and 8-aza-5-thia-16-arylPGE1 were synthesized and evaluated with respect to their subtype receptor affinity and EP4 agonist activity for the purposes of identifying sub-type- selective EP
Kambe, Tohru,Maruyama, Toru,Nakano, Masayuki,Yamaura, Yoshiyuki,Shono, Tomoyuki,Seki, Akiteru,Sakata, Kiyoto,Maruyama, Takayuki,Nakai, Hisao,Toda, Masaaki
experimental part
p. 1523 - 1534
(2012/01/13)

O -substituted alkyl aldehydes for rhodium-catalyzed intermolecular alkyne hydroacylation: The utility of methylthiomethyl ethers
Combining α-methylthiomethyl (MTM) ether substituted aldehydes and 1-alkynes in the presence of [Rh(dppe)]ClO4 results in efficient intermolecular alkyne hydroacylation to deliver α-O-MTM-substituted enone products. The product MTM ethers can be converted to the free hydroxyl group either in situ, by the addition of water to the completed reaction, or in a separate operation, by the action of silver nitrate.(Figure Presented)
Parsons, Scott R.,Hooper, Joel F.,Willis, Michael C.
supporting information; experimental part
p. 998 - 1000
(2011/05/15)

Polyunsaturated alkyl amides from echinacea: Synthesis of diynes, enynes, and dienes
The synthesis of 20 alkyl amides, including 15 naturally occurring polyunsaturated alkyl amides previously identified from Echinacea spp. (1-13 and 62) or from Achilla sp. (55) and five previously unknown geometric isomers (23, 28, 67, 73, and 80), is described. Importantly, these amides include all of the major alkyl amides present in commercially used Echinacea extracts. The syntheses demonstrate methodology used for constructing alkyl amides containing conjugated diyne and isomerically pure enyne and diene moieties and may be adapted easily for the preparation of other alkyl amides present in Echinacea spp. Terminal-conjugated diynes were prepared by a Cadiot-Chodkiewitz coupling/deprotection sequence utilizing a protected bromoacetylene, and methyl-substituted diynes were made via a base-catalyzed rearrangement of terminal-skipped diynes. Conjugated dienes were prepared conveniently and with high stereoselectivity by the reduction of enynes or diynes with Rieke zinc. With the exception of 1-2 and 11-12, the alkyl amides are synthesized here for the first time, and their NMR data are consistent with that of the reported isolated natural compounds.
Matovic, Nicholas J.,Hayes, Patricia Y.,Penman, Kerry,Lehmann, Reginald P.,De Voss, James J.
experimental part
p. 4467 - 4481
(2011/07/30)

Stereoselective synthesis of E,Z-configured 1,3-dienes by ring-closing metathesis. Application to the total synthesis of lactimidomycin
Strategic positioning of a silyl group on the diene unit of a diene-ene substrate allows rigorous regio- and stereocontrol to be exerted during metathesis-based macrocyclization reactions. The versatility of this concise approach to E,Z-configured 1,3-die
Gallenkamp, Daniel,Fuerstner, Alois
supporting information; experimental part
p. 9232 - 9235
(2011/08/06)

Syntheses, characterizations, and biological activities of tetradeca-4,8-dien-1-yl acetates as sex attractants of leaf-mining moth of the genus Phyllonorycter (Lepidoptera: Gracillariidae)
The four possible isomers of tetradeca-4,8-dien-1-yl acetate and corresponding alcohols were synthesized stereoselectively by synthetic routes employing Wittig coupling reaction for the preparation of (Z,E)- and (Z,Z)-isomers, and alkylation of terminal alkynes for the preparation of (E,E)- and (E,Z)-isomers as the key steps. Synthetic products were characterized by 13C- and 1H-NMR spectroscopy as well as mass-spectrometric methods. All four isomers gave distinctive mass spectra where m/z 81 fragments clearly dominated. Elution order, followed by retention index presented in parenthesis, of tetradeca-4,8-dien-1-ols was determined as (Z,Z) (2082.1), (Z,E) (2082.8), (E,E) (2083.1), and (E,Z) (2083.2) from unpolar SPB-1 column, and as (E,E) (2210.2), (Z,E) (2222.1), (E,Z) (2223.4), and (Z,Z) (2224.7) from polar DB-WAX column. The isomers of tetradeca-4,8-dien-1-yl acetates eluted in the order of (Z,Z) (2176.1), (Z,E) (2178.4), (E,Z) (2185.9), and (E,E) (2186.4) from SPB-1, and (Z,E) (2124.3), (E,E) (2157.7), (Z,Z) (2128.9), and (E,Z) (2135.9) from DB-WAX columns. Field-screening tests for attractiveness of tetradeca-4,8-dien-1-yl acetates revealed that (4Z,8E)-tetradeca-4,8-dien-1-yl acetate significantly attracted Phyllonorycter coryli and Chrysoesthia drurella males. (4E,8E)-Tetradeca-4,8-dien-1-yl acetate was the most efficient attractant for Ph. esperella and Ph. saportella males, and (4E,8Z)-tetradeca-4,8-dien-1-yl acetate was attractive to Ph. cerasicolella males.
Liblikas, Ilme,Mozuraitis, Raimondas,Santangelo, Ellen M.,Noreika, Remigijus,Borg-Karlson, Anna-Karin
experimental part
p. 1388 - 1403
(2010/04/23)

Cerulenin analogues as inhibitors of efflux pumps in drug-resistant candida albicans
Overexpression of the ABC transporters Cdrl and Cdr2 or the major facilitator Mdrl causes multidrug resistance in the human fungal pathogen Candida albicans. The fatty acid synthesis inhibitor cerulenin and the structurally unrelated Golgi transport inhibitor brefeldin A are substrates for both types of efflux pumps in Candida albicans. In an effort to overcome efflux pump-mediated drug resistance in Candida albicans, cerulenin analogues were generated using a variety of synthesis pathways. The so obtained cerulenin derivatives were tested on multidrug-resistant Candida albicans isolates which constitutively overexpress either Mdr1 or Cdr1 and Cdr2. Some of these compounds were found to decrease Mdr1-mediated resistance to brefeldin A up to eight-fold compared to the control. 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Diwischek, Florian,Morschhae, Joachim,Holzgrabe, Ulrike
scheme or table
p. 150 - 164
(2009/05/07)

Synthesis of tricyclic fused 3-aminopyridines through intramolecular Coi-catalyzed [2+2+2] cycloaddition between ynamides, nitriles, and alkynes
The first [2+2+2] cocyclizations between ynamides, nitriles, and alkynes are reported. They open a new access to unprecedented nitrogen-containing heterocycles of type 2-trimethylsilyl-3-aminopyridines. Such frameworks, which can be found in various compo
Garcia, Pierre,Moulin, Solenne,Mielo, Yves,Leboeuf, David,Gandon, Vincent,Aubert, Corinne,Malacria, Max
scheme or table
p. 2129 - 2139
(2009/09/06)

Regio- and stereoselective hydroamidation of 1-alkynylphosphine sulfides catalyzed by cesium base
(Chemical Equation Presented) Regio- and stereoselective hydroamidation of 1-alkynylphosphine sulfides proceeds in the presence of cesium carbonate to provide (E)-2-amino-1-thiophosphinyl-1-alkenes. Asymmetric hydrogenation of the adducts catalyzed by an
Kondoh, Azusa,Yorimitsu, Hideki,Oshima, Koichiro
supporting information; experimental part
p. 3093 - 3095
(2009/05/27)

Total synthesis of the resorcylic lactone-based kinase inhibitor L-783277
The total synthesis of the natural product L-783277 (1) has been accomplished based on the convergent assembly of building blocks 9, 10, and 14. Key steps are the Suzuki coupling of olefin 11 and aromatic building block 14, the Mitsunobu-based macrolac-to
Hofmann, Tatjana,Altmann, Karl-Heinz
scheme or table
p. 1500 - 1504
(2009/04/07)

Stereoselective synthesis, natural occurrence and CB2 receptor binding affinities of alkylamides from herbal medicines such as Echinacea sp.
A divergent synthesis of (2E,4E,8E,10E)- and (2E,4E,8E,10Z)-N- isobutyldodeca-2,4,8,10-tetraenamides from pent-4-yn-1-ol allowed identification of the (2E,4E,8E,10Z)-isomer for the first time in Echinacea species. A short, stereoselective synthesis of the (2E,4E,8E,10Z)-isomer is also described which allowed further biological evaluation of this material, and the demonstration that this isomer does not occur in Spilanthes mauritiana as previously reported. This journal is The Royal Society of Chemistry.
Matovic,Matthias,Gertsch, Juerg,Raduner, Stefan,Bone,Lehmann,DeVoss
p. 169 - 174
(2008/03/14)

Synthesis of (R)-japonilure and (4R,9Z)-9-octadecen-4-olide, pheromones of the Japanese beetle and currant stem girdler
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
p. 2491 - 2500
(2008/02/10)

Kinesin spindle protein (KSP) inhibitors. Part 6: Design and synthesis of 3,5-diaryl-4,5-dihydropyrazole amides as potent inhibitors of the mitotic kinesin KSP
3,5-Diaryl-4,5-dihydropyrazoles were discovered to be potent KSP inhibitors with excellent in vivo potency. These enzyme inhibitors possess desirable physical properties that can be readily modified by incorporation of a weakly basic amine. Careful adjust
Coleman, Paul J.,Schreier, John D.,Cox, Christopher D.,Fraley, Mark E.,Garbaccio, Robert M.,Buser, Carolyn A.,Walsh, Eileen S.,Hamilton, Kelly,Lobell, Robert B.,Rickert, Keith,Tao, Weikang,Diehl, Ronald E.,South, Vicki J.,Davide, Joseph P.,Kohl, Nancy E.,Yan, Youwei,Kuo, Lawrence,Prueksaritanont, Thomayant,Li, Chunze,Mahan, Elizabeth A.,Fernandez-Metzler, Carmen,Salata, Joseph J.,Hartman, George D.
p. 5390 - 5395
(2008/04/03)

In vivo studies of dialkynoyl analogues of DOTAP demonstrate improved gene transfer efficiency of cationic liposomes in mouse lung
A novel set of dialkynoyl analogues of the cationic, gene delivery lipid DOTAP (1) was synthesized. Structure-activity studies demonstrate that replacement of the cis-double bonds of DOTAP with triple bonds in varying positions alters both the physical properties of the resultant cationic liposome-DNA complexes and their biological functionalities, both in vitro and in vivo. Particularly, in vivo studies demonstrate that pDNA transfection of mouse lung endothelial cells with lead analogue DS(14-yne)TAP (4):cholesterol lipoplexes exhibits double the transfection level with less associated toxicity relative to the well-established DOTAP:cholesterol system. In fact, 4:cholesterol delivers up to 3 times the dose of pDNA in mice than can be tolerated by DOTAP, leading to nearly 3 times greater marker-gene expression. X-ray diffraction studies suggest that lipoplexes containing analogue 4 display increased stability at physiological temperatures. Our results thus suggest that analogue 4 is a potentially strong candidate for the gene therapy of lung tumors.
Fletcher, Steven,Ahmad, Ayesha,Perouzel, Eric,Heron, Andrew,Miller, Andrew D.,Jorgensen, Michael R.
p. 349 - 357
(2007/10/03)

A dialkynoyl analogue of DOPE improves gene transfer of lower-charged, cationic lipoplexes
Positively-charged gene delivery agents, such as cationic liposomes, typically prepared by mixing a cationic lipid and a neutral lipid in a 1: 1 molar ratio, exhibit a fundamental flaw: on the one hand, the charge encourages cell uptake; on the other hand, the charge leads to aggregation in vivo with anionic serum components. We herein report a more phase-stable analogue of the zwitterionic and fusogenic lipid DOPE that allows for the reduction of the cationic lipid component of the liposome from 50 to 9 mol% with almost no apparent loss in transfection activity. This reduction in charge may induce important in vivo stability whilst still imparting high cell uptake and transgene expression. The Royal Society of Chemistry 2006.
Fletcher, Steven,Ahmad, Ayesha,Perouzel, Eric,Jorgensen, Michael R.,Miller, Andrew D.
p. 196 - 199
(2007/10/03)

A silyl-mediated [3+2] photochemical cycloaddition
The generation of larger rings from intermediate cyclobutanes via a two-step [2+2] photocycloaddition - ring expansion, known as the de Mayo reaction, has been widely applied in synthesis. Herein a one-step synthesis of cyclopentanoids has been developed
Organ, Michael G.,Mallik, Debasis
p. 1259 - 1262
(2008/01/27)

MITOTIC KINESIN INHIBITORS
The present invention relates to tricyclic pyrazoles that are useful for treating cellular proliferative diseases, for treating disorders associated with KSP kinesin activity, and for inhibiting KSP kinesin. The invention also relates to compositions whic
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Page/Page column 45-47

(2008/06/13)

Radical cyclizations leading to the bicyclo[2.2.1]heptane framework: A new radical approach to (±)-(Z)-β-santalol
Tandem radical cyclizations of acyclic iodides, including [3-(2-iodoethyl)-6,10-dimethyl-undeca-5,9-dien-1-ynyl]-dimethylphenylsilane lead in good yields to bicyclo[2.2.1]heptane derivatives. The cascade relies on two sequential radical-mediated 5-exo-cyclizations. The radical approach is illustrated with the total synthesis of racemic-(Z)-β-santalol. The results are remarkable, two fused rings and one stereogenic center are formed in a single operation. A new 'coordinated' hydride appeared to be useful in the cascade.
Pianowski, Zbigniew,Rupnicki, Leszek,Cmoch, Piotr,Staliński, Krzysztof
p. 900 - 904
(2007/10/03)

Total synthesis of (±)-ceratopicanol: Application of Pd-catalyzed enediyne cycloreduction
Pd-catalyzed cycloreduction of enediyne 3 successfully afforded the linear triquinane skeleton 4. Total synthesis of (±)-ceratopicanol was accomplished using additional eight-step transformations starting from 4. Georg Thieme Verlag Stuttgart.
Oh, Chang Ho,Rhim, Chul Yun,Kim, Mira,Park, Dai In,Gupta, Aruna Kumar
p. 2694 - 2696
(2007/10/03)

Rh(I)-catalyzed CO gas-free cyclohydrocarbonylation of alkynes with formaldehyde to α,β-butenolides
The rhodium(I)-catalyzed reaction of alkynes with formaldehyde proceeds via the double incorporation of a carbonyl moiety from formaldehyde, resulting in a CO gas-free cyclohydrocarbonylation leading to α,β-butenolides. The Royal Society of Chemistry 2005.
Fuji, Koji,Morimoto, Tsumoru,Tsutsumi, Ken,Kakiuchi, Kiyomi
p. 3295 - 3297
(2007/10/03)

Fluorescence-labeled sphingosines as substrates of sphingosine kinases 1 and 2
Fluorescently labeled D-erythro-sphingosines have been successfully synthesized in 9 and 12 steps starting from commercially available Garner aldehyde. Determining the influence of the nature, position and linkage of the label on the in vitro phosphorylation rate by sphingosine kinases 1 and 2 resulted in the identification of a pyrene- and a NBD-labeled sphingosine which are both phosphorylated with efficiency comparable to the natural substrate.
Ettmayer, Peter,Billich, Andreas,Baumruker, Thomas,Mechtcheriakova, Diana,Schmid, Heide,Nussbaumer, Peter
p. 1555 - 1558
(2007/10/03)

ACETYLENIC ALPHA-AMINO ACID-BASED SULFONAMIDE HYDROXAMIC ACID TACE INHIBITORS
Compound of the formula (B) are useful in treating disease conditions mediated by TNF- alpha , such as rheumatoid arthritis, osteoarthritis, sepsis, AIDS, ulcerative colitis, multiple sclerosis, Crohn's disease and degenerative cartilage loss.
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Page 101

(2010/02/07)

Anomeric oxygen to carbon rearrangements of alkynyl tributylstannane derivatives of furanyl (γ)- and pyranyl (δ)-lactols
Tetrahydropyran and tetrahydrofuran containing natural products, drugs and agrochemicals often possess carbon-carbon bonds adjacent to the heteroatom. Consequently, new methods for the construction of anomeric carbon-carbon bonds are of considerable importance. We have devised a new strategy to access these systems that requires the treatment of O-glycoside alkynyl tributylstannane derivatives of furanyl and pyranyl lactols with Lewis acid to effect oxygen to carbon rearrangements. This leads to the formation of the corresponding carbon linked alkynol products that can be further manipulated to produce key structural motifs and building blocks for the assembly of complex molecules.
Buffet, Marianne F.,Dixon, Darren J.,Ley, Steven V.,Reynolds, Dominic J.,Storer, R. Ian
p. 1145 - 1154
(2007/10/03)

FUNGAL CELL WALL SYNTHESIS GENE
A reporter system reflecting the transport process that transports GPI-anchored proteins to the cell wall was constructed and compounds inhibiting this process were discovered. Further, genes conferring resistance to the above compounds were identified and methods of screening for compounds that inhibit the activity of the proteins encoded by these genes were developed.Therefore, through the novel compounds, the present invention showed that antifungal agents having a novel mechanism, i.e. inhibiting the process that transports GPI-anchored proteins to the cell wall, could be achieved.
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(2008/06/13)

Synthesis and characterization of hexadecadienyl compounds with a conjugated diene system, sex pheromone of the persimmon fruit moth and related compounds
Hexadecadien-1-ol and the derivatives (acetate and aldehyde) with a conjugated diene system have recently been identified from a pheromone gland extract of the persimmon fruit moth (Stathmopoda masinissa), a pest insect of persimmon fruits distributed in
Nishida, Takanobu,Vang, Le Van,Yamazawa, Hiroyuki,Yoshida, Ryuji,Naka, Hideshi,Tsuchida, Koji,Ando, Tetsu
p. 822 - 829
(2007/10/03)

Electrotelluration: A new approach to tri- and tetrasubstituted alkenes
A novel electrotelluration process is described in which a Michael addition of an alkyl or aryl tellurolate anion occurs onto an activated alkyne with subsequent trapping of a vinyl anion with electrophiles (aldehydes and ketones) other than a proton. This process provides an efficient regio-and stereospecific route to tri- and tetrasubstituted alkenes. Methodologically significant examples of this chemistry were studied in which aryl and alkyl tellurolate anions were added to ω-keto alkynyl esters in a Michael reaction, and the incipient vinyl anions were trapped intramolecularly by the internal aldehydes. The reactive centers were tethered by different lengths of alkyl chains to form highly functionalized five-, six-, seven-, and eight-membered rings in modest to good yields.
Marino, Joseph P.,Nguyen, Hanh Nho
p. 6291 - 6296
(2007/10/03)

Nitrone dipolar cycloaddition routes to piperidines and indolizidines. Part 9. Formal synthesis of (-)-pinidine and total synthesis of (-)-histrionicotoxin, (+)-histrionicotoxin and (-)-histrionicotoxin 235A
An intramolecular hydroxylamine-alkyne cyclisation is used for the enantioselective synthesis of the cyclic nitrones 36 and 44. We have demonstrated the use of a novel nitrone protection strategy by cycloaddition of styrene to the cyclic nitrone 44 in the synthesis of the spirocyclic core of the histrionicotoxin family of alkaloids. Deprotection by dipolar cycloreversion of the styrene adduct (the bicyclic isoxazolidine 39) and in situ intramolecular dipolar cycloaddition of a pendant (Z)-α,β-unsaturated nitrile to the intermediate nitrone 50 gave the isoxazolidine 51 in high yield with a surprising degree of regioselectivity compared with the corresponding (Z)-enyne 36. The method is amenable to the synthesis of both enantiomers 51 and 62 of the tricyclic core structure which can be converted by way of the common intermediates (e.g. 53 and ent-53) respectively into the natural configuration of alkaloids (-)-histrionicotoxin 1 and (-)-histrionicotoxin 235A 65 as well as the unnatural (+)-histrionicotoxin 63.
Davison, Edwin C.,Fox, Martin E.,Holmes, Andrew B.,Roughley, Stephen D.,Smith, Catherine J.,Williams, Geoffrey M.,Davies, John E.,Raithby, Paul R.,Adams, Joseph P.,Forbes, Ian T.,Press, Neil J.,Thompson, Mervyn J.
p. 1494 - 1514
(2007/10/03)

A fast and practical approach to tetrahydropyranylation and depyranylation of alcohols using indium triflate
Indium triflate-mediated tetrahydropyranylation of alcohols in dichloromethane and depyranylation of these products in aqueous methanol utilizing the same reagent but different molar ratio is described. In addition, indium triflate-promoted conversion of tetrahydropyran ethers to their corresponding acetates has also been described.
Mineno, Tomoko
p. 7975 - 7978
(2007/10/03)

1,2-Silyl-migrative cyclization of vinylsilanes bearing a hydroxy group: Stereoselective synthesis of multisubstituted tetrahydropyrans and tetrahydrofurans
Acid-catalyzed intramolecular addition of a hydroxy group to α-alkylated vinylsilanes has been studied. Treatment of (Z)-5-alkyl-5-silyl-4-penten-1-ols 1 (R = alkyl) with 5 mol % TiCl4 in CHCl3 gave trans-2-alkyl-3-silyltetrahydropyrans 2 exclusively (trans/cis = > 99/1 to 97/3). The cyclization efficiency and rate strongly depended on the geometry of the C-C double bond and the silyl group. The use of (E)-vinylsilanes resulted in lower yields with poor cis-selectivity. In the cyclization of (Z)-1 (R = Bu), the silyl group used, the reaction time, and the yield of 2 were as follows: SiMe2Ph, 9.5 h, 75%; SiMe3, 7.5 h, 66%; SiMePh2, 24 h, 58%; SiMe2-t-Bu, 0.75 h, 85%; SiMe2Bn, 1.5 h, 78%. This 1,2-silyl-migrative cyclization could be applied to stereoselective synthesis of trisubstituted tetrahydropyrans. The acid-catalyzed reaction of 1-, 2-, or 3-substituted (Z)-5-silyl-4-nonen-1-ols 8 gave r-2,t-3,c-6-, r-2,t-3,t-5-, or r-2,t-3,c-4-trisubstituted tetrahydropyrans with high diastereo-selectivity, respectively. (Z)-4-Alkyl-4-silyl-3-buten-1-ols 5 as well as 1 underwent the 1,2-silylmigrative cyclization to give 2-alkyl-3-silyltetrahydrofurans 6 with high trans-selectivity. This silicon-directed cyclization was also available for the stereoselective synthesis of tri- and tetrasubstituted tetrahydrofurans.
Miura, Katsukiyo,Hondo, Takeshi,Okajima, Shigeo,Nakagawa, Takahiro,Takahashi, Tatsuyuki,Hosomi, Akira
p. 6082 - 6090
(2007/10/03)

Study of the regioselectivity in the hydrotelluration of hydroxy alkynes
Vinylic tellurides were synthesized by the addition of organotellurols to acetylenic alcohols and the regioselectivity of the reaction was evaluated.
Stefani, Hélio A.,Cardoso, Lincoln D. G.,Valduga, Claudéte J.,Zeni, Gilson
p. 167 - 172
(2007/10/03)

A convergent asymmetric synthesis of γ-butenolides
The addition of aldehydes to the new enantiomerically pure lithiated sulfoxide-orthoester 13 yielded γ-butenolides of high enantiomeric purities after elimination of phenylsulfinic acid. The cyclocondensation with ketones was less stereoselective. This new asymmetric synthesis of γ-butenolides has been applied to a convergent preparation of the antifungal antibiotic (+)-cerulenin.
Renard, Marc,Ghosez, Léon A.
p. 2597 - 2608
(2007/10/03)