- β-Selective nucleoside analog synthesis from chlorofuranoses
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A method to form glycosyl linkages between nitrogen-containing heterocycles and appropriately protected furanoses is described. The method is highly beta-selective, operationally simple, and utilizes readily available reagents making the process amenable to scaleup. Representative examples of coupling between chlorofuranoses and purines or pyrrolopyrimidines are described. (C) 2000 Published by Elsevier Science Ltd.
- Scott,Fox,Williams
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Read Online
- Correlation study between A3 adenosine receptor binding affinity and anti-renal interstitial fibrosis activity of truncated adenosine derivatives
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Truncated 4′-thionucleosides 1–4 and 4′-oxonucleosides 5–8 as potent and selective A3AR antagonists were synthesized from d-mannose and d-erythronic acid γ-lactone, respectively. These nucleosides were evaluated for their anti-fibrotic renoprot
- Yu, Jinha,Kim, Gyudong,Jarhad, Dnyandev B.,Lee, Hyuk Woo,Lee, Jiyoun,Park, Chong Woo,Ha, Hunjoo,Jeong, Lak Shin
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p. 773 - 779
(2018/10/09)
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- SUBSTITUTED NUCLEOSIDE DERIVATIVES USEFUL AS ANTICANCER AGENTS
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Compounds of the general formula (I): processes for the preparation of these compounds, compositions containing these compounds, and the uses of these compounds.
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Paragraph 0339; 0340
(2016/09/26)
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- Syntheses of arabinose-derived pyrrolidine catalysts and their applications in intramolecular Diels-Alder reactions
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Six chiral hydroxylated pyrrolidine catalysts were synthesized from commercially available D-arabinose in seven steps. Various aromatic substituents α to the amine can be introduced readily by a Grignard reaction, which enables facile optimization of the catalyst performance. The stereoselectivities of these catalysts have been assessed by comparing with those of MacMillan's imidazolidinone in a known intramolecular Diels-Alder (IMDA) reaction of a triene. Two additional IMDA reactions of symmetrical dienals with concomitant desymmetrisation further established the potential use of these novel amine catalysts. These pyrrolidines are valuable catalysts for other synthetic transformations.
- Shing, Tony K. M.,Wu, Kwun W.,Wu, Ho T.,Xiao, Qicai
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p. 1754 - 1762
(2015/02/19)
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- Doubly diastereoselective conjugate additions of the antipodes of lithium N-benzyl-N-(α-methylbenzyl)amide to enantiopure ε-O-protected α,β-unsaturated esters derived from d-ribose
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Enantiopure ε-O-silyloxy- and ε-O-benzyloxy-α,β- unsaturated esters derived from d-ribose, each containing a cis-dioxolane unit, display excellent (≥95:5 dr) levels of diastereofacial directing ability upon conjugate addition of achiral lithium N-benzyl-N-isopropylamide. In contrast to the corresponding enantiopure ε-O-silyloxy-α,β-unsaturated ester derived from l-tartaric acid, which contains a trans-dioxolane unit, the conjugate additions of the antipodes of lithium N-benzyl-N-(α- methylbenzyl)amide to its cis-configured counterpart result in doubly diastereoselective 'matched' and 'mismatched' reaction pairings in which the inherent reagent control serves to augment or oppose, respectively, the established substrate diastereocontrol.
- Davies, Stephen G.,Foster, Emma M.,Lee, James A.,Roberts, Paul M.,Thomson, James E.
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p. 534 - 546
(2014/05/06)
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- Synthesis of carbohydrates in mineral-guided prebiotic cycles
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One present obstacle to the "RNA-first" model for the origin of life is an inability to generate reasonable "hands off" scenarios for the formation of carbohydrates under conditions where they might have survived for reasonable times once formed. Such scenarios would be especially compelling if they deliver pent(ul)oses, five-carbon sugars found in terran genetics, and exclude other carbohydrates (e.g., aldotetroses) that may also be able to function in genetic systems. Here, we provide detailed chemical analyses of carbohydrate premetabolism, showing how borate, molybdate, and calcium minerals guide the formation of tetroses (C4H8O4), heptoses (C7H14O7), and pentoses (C 5H10O5), including the ribose found in RNA, in "hands off" experiments, starting with formaldehyde and glycolaldehyde. These results show that pent(ul)oses would almost certainly have formed as stable borate complexes on the surface of an early Earth beneath a humid CO2 atmosphere suffering electrical discharge. While aldotetroses form extremely stable complexes with borate, they are not accessible by pathways plausible under the most likely early Earth scenarios. The stabilization by borate is not, however, absolute. Over longer times, material is expected to have passed from borate-bound pent(ul)oses to a branched heptulose, which is susceptible to Cannizzaro reduction to give dead end products. We show how this fate might be avoided using molybdate-catalyzed rearrangement of a branched pentose that is central to borate-moderated cycles that fix carbon from formaldehyde. Our emerging understanding of the nature of the early Earth, including the presence of hydrated rocks undergoing subduction to form felsic magmas in the early Hadean eon, may have made borate and molydate species available to prebiotic chemistry, despite the overall "reduced" state of the planet.
- Kim, Hyo-Joong,Ricardo, Alonso,Illangkoon, Heshan I.,Kim, Myong Jung,Carrigan, Matthew A.,Frye, Fabianne,Benner, Steven A.
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experimental part
p. 9457 - 9468
(2011/08/04)
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- Stereochemistry of enacyloxins. Part 6: Synthesis of C16′-C23′ fragments of enacyloxins, a series of antibiotics from Frateuria sp. W-315
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The C16′-C23′ fragments of enacyloxins, a series of antibiotics isolated from Frateuria sp. W-315, were synthesized from D-arabinose. Copyright by Walter de Gruyter Berlin Boston.
- Igarashi, Wataru,Hoshikawa, Hiroaki,Furukawa, Hiroyuki,Yamada, Teiko,Kuwahara, Shigefumi,Kiyota, Hiromasa
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scheme or table
p. 7 - 9
(2011/10/18)
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- Use of the NEO strategy (Nucleophilic addition/Epoxide Opening) for the synthesis of a new C-galactoside ester analogue of KRN 7000
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Our goal in the search for potentially bioactive analogues of KRN 7000 was to design an easy synthetic approach to a library of analogues using a strategy recently developed in our laboratory based on a Nucleophilic addition followed by an Epoxide Opening
- Banchet-Cadeddu, Aline,Martinez, Agathe,Guillarme, Stéphane,Parietti, Véronique,Monneaux, Fanny,Hénon, Eric,Renault, Jean-Hugues,Nuzillard, Jean-Marc,Haudrechy, Arnaud
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supporting information; experimental part
p. 2510 - 2514
(2011/06/11)
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- Structure-activity relationships of truncated adenosine derivatives as highly potent and selective human A3 adenosine receptor antagonists
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On the basis of potent and selective binding affinity of truncated 4′-thioadenosine derivatives at the human A3 adenosine receptor (AR), their bioisosteric 4′-oxo derivatives were designed and synthesized from commercially available 2,3-O-isopr
- Pal, Shantanu,Choi, Won Jun,Choe, Seung Ah,Heller, Cara L.,Gao, Zhan-Guo,Chinn, Moshe,Jacobson, Kenneth A.,Hou, Xiyan,Lee, Sang Kook,Kim, Hea Ok,Jeong, Lak Shin
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experimental part
p. 3733 - 3738
(2009/10/02)
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- N-Substituent effects on the diethylzinc addition to benzaldehyde catalysed by bicyclic 1,4-amino alcohols
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Chiral enantiopure bicyclic 1,4-amino alcohols were synthesised by a new methodology that provided a common precursor, which was easily N-functionalised with a wide variety of substituents. The final compounds were used as chiral ligands in a model study of the enantioselective addition of diethyl zinc to benzaldehyde, aimed at understanding the influence of the N-substituent on both the rate and stereoselectivity of the reaction. This set of experiments also provided interesting insight into the non-catalysed addition that occurred by employing commercially available Et2Zn solutions.
- Scarpi, Dina,Occhiato, Ernesto G.,Guarna, Antonio
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experimental part
p. 340 - 350
(2009/09/05)
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- Carbon-branched carbohydrate chirons: synthesis of C-3 and C-4-branched sugar lactones derived from d-erythronolactone
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Two carbon chain extensions using a Wittig reaction on both a 1-deoxy ribulose derivative and a C-2-branched erythrose derivative are reported. Subsequent dihydroxylation resulted in the synthesis of C-3 and C-4 methyl-branched sugar lactones, the useful
- Jenkinson, Sarah F.,Victoria Booth,Estevez Reino, Amalia M.,Horne, Graeme,Estevez, Ramon J.,Fleet, George W.J.
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experimental part
p. 2357 - 2367
(2010/03/24)
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- An unexpectedly facile cyclization of polyhydric alcohols
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Image Presented Contrary to previous reports in the literature, the reaction of polyhydric alcohols such as sorbitol or mannitol gives good yields of the tetrahydroxyoxepane derivative in the presence of an acid catalyst, in refluxing toluene, with complete retention of stereochemistry.
- Pavlik, Christopher,Onorato, Amber,Castro, Steve,Morton, Martha,Peczuh, Mark,Smith, Michael B.
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supporting information; experimental part
p. 3722 - 3725
(2011/02/28)
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- An efficient and practical total synthesis of aigialomycin D
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An efficient and practical total synthesis of aigialomycin D 1 is described. This concise synthetic route features the use of readily available starting materials with the key transformations being the formation of the macrocycle by RCM under microwave ir
- Vu, Nguyen Quang,Chai, Christina L.L.,Lim, Kok Peng,Chia, Sze Chen,Chen, Anqi
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p. 7053 - 7058
(2008/02/05)
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- Isolation, structure elucidation, total synthesis, and evaluation of new natural and synthetic ceramides on human SK-MEL-1 melanoma cells
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Two new long-chain ceramides, trametenamides A (1) and B (2), were isolated from the methanolic extract of the fruiting body of the fungus Trametes menziesii. The structures were elucidated by spectroscopic analyses and chemical transformations, and the absolute stereochemistry of trametenamide B (2) was determined by stereoselective total synthesis of four possible diastereomers. The acetyl derivative of the natural ceramide (1a) and synthetic ceramides (24-27) showed cytotoxicity on the human melanoma cell line SK-MEL-1, which was caused by induction of apoptosis as determined by DNA fragmentation, poly-(ADP-ribose) polymerase cleavage, and procaspase-9 and -8 processing.
- León, Francisco,Brouard, Ignacio,Rivera, Augusto,Torres, Fernando,Rubio, Sara,Quintana, José,Estévez, Francisco,Bermejo, Jaime
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p. 5830 - 5839
(2007/10/03)
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- PURINE DERIVATIVES AS A3 AND A1 ADENOSINE RECEPTOR AGONISTS
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Disclosed are (N)-methanocarba adenine nucleosides of the formula: [Formula] as highly potent A3 adenosine receptor agonists, pharmaceutical compositions comprising such nucleosides, and a method of use of these nucleosides, wherein R1-R6 are as defined in the specification. These nucleosides are contemplated for use in the treatment a number of diseases, for example, inflammation, cardiac ischemia, stroke, asthma, diabetes, and cardiac arrhythmias. The invention also provides compounds that are agonists of both A1 and A3 adenosine receptors for use in cardioprotection.
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Page/Page column 19
(2010/10/20)
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- Highly active chiral ruthenium catalysts for asymmetric cross- and ring-opening cross-metathesis
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Metathesis takes sides: The scope of asymmetric metathesis has been expanded with the use of chiral ruthenium catalysts for asymmetric ring-opening cross-metathesis and for the first example of an asymmetric cross-metathesis (see scheme, TIPS = triisoprop
- Berlin, Jacob M.,Goldberg, Steven D.,Grubbs, Robert H.
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p. 7591 - 7595
(2008/02/01)
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- Total synthesis and antiangiogenic activity of cyclopentane analogues of fumagillol
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Novel cyclopentane analogues of fumagillol were synthesized and their endothelial cell proliferation inhibitory activities were evaluated. The cyclopentane-fumagillol derivatives were synthesized from (-)-2,3-O- isopropylidene-d-erythronolactone via stereoselective glycolate Claisen rearrangement and intramolecular ester enolate alkylation as key steps.
- Jeong, Byeong-Seon,Nam, Song Choi,Soon, Kil Ahn,Bae, Hoon,Hak, Sung Kim,Kim, Deukjoon
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p. 3580 - 3583
(2007/10/03)
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- A new synthetic route to (North)-methanocarba nucleosides designed as A3 adenosine receptor agonists
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(Chemical Equation Presented) Activation of the A3 adenosine receptor (AR) is associated with cerebroprotective, cardioprotective, and anticancer effects. Among potent and selective A3 AR agonists are novel methanocarba adenosine analogues in which the conformation of a pseudo-ribose moiety is locked in the North (N) hemisphere of the pseudorotational cycle. 5′-Uronamide (N)-methanocarba nucleosides, such as MRS1898 and MRS2346, are examples of full agonists of the human A3 AR. An improved convergent approach from easily accessible 2,3-O-isopropylidene- D-erythrose (2b), and the combination of a strategic intramolecular cyclopropanation step plus the acid-catalyzed isomerization of an isopropylidene group, provided a suitable pseudosugar precursor (23) for the synthesis of MRS1898, MRS2346, and related analogues. This new synthetic route uses readily available building blocks and opens the way for the preparation of a variety of targets on a reasonable scale.
- Joshi, Bhalchandra V.,Hyung, Ryong Moon,Fettinger, James C.,Marquez, Victor E.,Jacobson, Kenneth A.
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p. 439 - 447
(2007/10/03)
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- Pd-catalyzed nucleophilic allylic alkylation of aliphatic aldehydes by the use of allyl alcohols
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Under catalysis of Pd(OAc)2-(P-n-Bu)3, Et 2Zn promotes a variety of allyl alcohols to undergo nucleophilic allylation of aliphatic aldehydes and ketones at room temperature and provides homoallyl alcohols in 60-90 and ca. 60% isolated yield, respectively. The reaction is irreversible and kinetically controlled, and unique regio- and stereoselectivities observed for the allylation with unsymmetrically substituted allyl alcohols are discussed.
- Kimura, Masanari,Shimizu, Masamichi,Tanaka, Shuji,Tamaru, Yoshinao
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p. 3709 - 3718
(2007/10/03)
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- Use of allyl, 2-tetrahydrofuryl, and 2-tetrahydropyranyl ethers as useful C3-, C4-, and C5-carbon sources: Palladium-catalyzed allylation of aldehydes
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Palladium-diethylzinc or palladium-triethylborane catalytically promotes self-allylation of 2-(allyloxy)tetrahydrofurans, 2-(allyloxy)tetrahydropyrans, and their hydroxy derivatives on the rings (ribose, glucose, mannose, deoxyribose, deoxyglucose). All the reactions proceed at room temperature and provide polyhydroxyl products, sharing a structural motif of a homoallyl alcohol, in good to excellent yields with high levels of stereoselectivity. Useful Crunit elongation, which makes the best use of an allyl ether as a protecting group and a nucleophilic allylation agent, is demonstrated. Mechanisms for the umpolung reaction (of an allyl ether into an allylic anion) and stereoselectivity associated with allylation of aldehydes are discussed.
- Shimizu, Masamichi,Kimura, Masanari,Tamaru, Yoshinao
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p. 6629 - 6642
(2007/10/03)
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- 1-Deoxy-D-xylulose: Synthesis based on molybdate-catalyzed rearrangement of a branched-chain aldotetrose
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equation presented 1-Deoxy-D-xylulose has been prepared in seven steps and ~21% overall yield from 2,3-O-isopropylidene-D-erythrono-1,4-lactone. The key reaction involves transformation of a branched-chain aldotetrose to the 1-deoxy-2-ketopentose catalyze
- Zhao, Shikai,Petrus, Ladislav,Serianni, Anthony S.
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p. 3819 - 3821
(2007/10/03)
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- Synthesis of the kedarcidin core structure by a transannular cyclization pathway
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The chromoprotein enediyne antibiotic kedarcidin has a structurally complex and highly reactive chromophore component. An enantioselective synthesis of compound 1, which contains the full functionality of the chromophore core, is described. The key step in the synthetic route involves low-temperature halogen-lithium exchange initiated transannular cyclization of the macrocyclic vinyl bromide 2. TBS = tert-butyldimethylsilyl.
- Myers, Andrew G.,Goldberg, Steven D.
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p. 2732 - 2735
(2007/10/03)
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- A ring closing metathesis-osmylation approach to oxygenated oxepanes as carbohydrate surrogates
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A ring closing metathesis (RCM)-osmylation sequence has been developed for the formation of highly oxygenated cyclic ethers from the corresponding acyclic dienes. A systematic examination of various substrates in this reaction revealed that the process is general in scope and is insensitive to the number of alkoxy substituents present. Subsequent osmylation of the metathesis product proceeds with excellent diastereoselectivity to furnish highly oxygenated oxepanes. These oxepanes represent one-carbon homologated carbohydrates.
- Wong, Jerome C. Y.,Lacombe, Patrick,Sturino, Claudio F.
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p. 8751 - 8754
(2007/10/03)
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- D-erythronolactone as a C4 building unit. Part 2.1 a short and efficient synthesis of both enantiomers of epi-muricatacin, a diastereoisomer of the native acetogenin from Annona muricata
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Both enantiomers of epi-muricatacin (+)- and (-)-2 have been prepared from 2,3-O-isopropylidene-D-erythrose 7. The enantiomers (+)- and (-)-2 are obtained in good yields and with high diastereoisomeric and enantiomeric purity. The aim of the synthesis is to obtain both enantiomers of the target molecule from one chiral precursor. This was made possible by the reaction sequence for the introduction of the two different side chains being exchangeable.
- Gypser, Andreas,Peterek, Marcus,Scharf, Hans-Dieter
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p. 1013 - 1016
(2007/10/03)
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- Microbial Oxidation of Chloroaromatics in the Enantiodivergent Synthesis of Pyrrolizidine Alkaloids: Trihydroxyheliotridanes
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Both enantiomers of the pyrrolizidine alkaloid trihydroxyheliotridane 1 have been prepared in an efficient and stereocontrolled fashion in 10 steps.Key steps involve the microbial oxidation of chlorobenzene with Pseudomonas putida to afford chiral cyclohexadienediol 4 with high enantiomeric excess and its conversion to lactone 7, from which either enantiomer of azide 18 can be prepared.The azides are converted to the title compounds via a pyrroline annulation based on an intramolecuular azide-diene cycloaddition/thermal rearrangement.
- Hudlicky, Tomas,Luna, Hector,Price, John D.,Rulin, Fan
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p. 4683 - 4687
(2007/10/02)
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- AN ENANTIODIVERGENT APPROACH TO D- AND L-ERYTHROSE VIA MICROBIAL OXIDATION OF CHLOROBENZENE
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D- and L-erythrose derivatives have been synthesized from chlorobenzene, providing for the conversion of undesired pollutants to synthetically useful chiral intermediates.The overall yields of the title compounds are compared to known preparation from ara
- Hudlicky, Tomas,Luna, Hector,Price, John D.,Rulin, Fan
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p. 4053 - 4054
(2007/10/02)
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- GAS CHROMATOGRAPHY - MASS SPECTROMETRY OF OSULOSE DERIVATIVES: O-TRIMETHYLSILYL, O-ACETYL, O-ISOPROPYLIDENE, METHYL GLYCOSIDES, AND 1,1-DIMETHYL ACETALS
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Structure determination of the O-trimethylsilyl, O-acetyl, and O-isopropylidene derivatives of some hexuloses, pentuloses, and one tetrulose, as well as their methyl glycosides and 1,1-dimethyl acetals has been achieved by gas chromatography - mass spectrometry.By study based on the qualitative and quantitative differences in the 36 derivatives obtained, and their analogues prepared from tetradeuterio methanol and/or hexadeuterio acetone, and comparison with results reported in the literature, criteria for the unambiguouos determination of the structural grouping are proposed.The relative abundance of each compound when the osulose forms more than one isomeric derivative in the same reaction, as well as chromatographic data for the isolated products, are reported.
- Ruiz, Pedro Antonio Garcia,Travesedo, Immaculada Cartagena,Martinez, Antonio Soler
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p. 870 - 877
(2007/10/02)
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- Synthesis of optically active leukotriene (SRS-A) intermediates
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In an approach to SRS-A and analogues thereof, the key (5S, 6S)-epoxy alcohol 9 and its 6-epimer 18 were prepared starting from D-araboascorbic acid and L-diethyl tartrate, respectively.
- Cohen, Noal,Banner, Bruce L.,Lopresti, Rocco J.
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p. 4163 - 4166
(2007/10/02)
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