- MEAYAMYCIN ANALOGUES AND METHODS OF USE
-
Compounds according to formula (I), where R is as defined herein, have anti-cancer properties.
- -
-
Page/Page column 5
(2021/10/15)
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- BIOMARKER PANEL TARGETED TO DISEASES DUE TO MULTIFACTORIAL ONTOLOGY OF GLYCOCALYX DISRUPTION
-
The present disclosure provides biomarkers useful as companion diagnostics for detecting glycocalyx-based disease that is amenable to treatment using compounds designed for improving the condition of the glycocalyx and/or reducing inflammation and/or oxidative damage, as well as related compositions, kits, and methods.
- -
-
-
- Preparation method of ticagrelor key intermediate iodide
-
The invention discloses a preparation method of ticagrelor key intermediate iodide, which comprises the following steps of: (1) synthesis of an intermediate 1: taking D-ribose as a raw material, methanol and acetone as solvents, adding thionyl chloride as a catalyst, and concentrating to remove the solvents after the reaction is finished, so as to obtain the intermediate 1, and (3) synthesis of the key intermediate iodide: by taking acetonitrile as a solvent, adding the intermediate 1 and sodium iodide into a reaction system, dropwise adding trimethylchlorosilane, adding a small amount of water for quenching reaction after the reaction is finished, evaporating to remove acetonitrile, extracting with the solvent, and concentrating to obtain the key intermediate iodide. According to the preparation method of the ticagrelor key intermediate iodide, in the synthesis process of the intermediate 1, thionyl chloride is adopted to replace hydrochloric acid to serve as a catalyst, the reactionconversion rate is greatly increased, then trimethylchlorosilane/sodium iodide serves as an iodinating agent, the reaction condition is mild, aftertreatment is simple, and the conversion rate is high.
- -
-
Paragraph 0038-0043
(2020/05/01)
-
- Total Synthesis of Meayamycin and O-Acyl Analogues
-
A short, scalable total synthesis of meayamycin is described by an approach that entails a longest linear sequence of 12 steps (22 steps overall) from commercially available chiral pool materials (ethyl l-lactate, BocNH-Thr-OH, and d-ribose) and introduces the most straightforward preparation of the right-hand subunit detailed to date. The use of the approach in the divergent synthesis of a representative series of O-acyl analogues is exemplified.
- Boger, Dale L.,Chanda, Prem B.,Chowdari, Naidu S.,Gangwar, Sanjeev,Gartshore, Christopher,Momirov, Jelena,Sarkar, Anindya,Tadano, Shinji,Vite, Gregory D.,Zhang, Qian
-
-
- Industrial large-scale production method of capecitabine intermediate
-
The invention provides an industrial large-scale production method of a capecitabine intermediate. The industrial large-scale production method adopts a one-pot production method of simultaneously adding methanol and acetone, and is a preparation method which is energy-saving, short in production period and high in yield; a method of adding low-boiling-point solvents such as ethyl acetate into dimethyl sulfoxide or pyrrolidone for reflux cooling to take away heat is adopted; and a production method of hydrolyzing while distilling is designed, the methanol and the acetone which are generated byhydrolysis are distilled out, the methanol and the acetone in water are continuously reduced, the reaction is carried out towards K3, and the reaction is complete and thorough.
- -
-
Paragraph 0041; 0042
(2020/09/20)
-
- Tumor immunity compound and application thereof
-
Disclosed are a tumor immunity compound and an application thereof. The invention discloses a compound as shown in the formula (I), optical isomers thereof, and pharmaceutically acceptable salts thereof, and an application of the compound as an STING agonist.
- -
-
Paragraph 0662; 0663-0667
(2020/07/14)
-
- A novel and environmental friendly synthetic route for hydroxypyrrolidines using zeolites
-
A critical step in the synthesis of the hydroxypyrrolidines, 1,4-dideoxy-1,4-imino-L-lyxitol and 1,4-dideoxy-1,4-imino-D-lyxitol, from the corresponding D-sugars is the synthesis of O-methyl 2,3-O-isopropylidenepentofuranoses. Instead of applying homogeneous catalysis process with conventional inorganic acid catalysts like HCl and HClO4, it was found that heterogeneous catalysis using zeolites could be used for the one-pot synthesis of O-methyl 2,3-O-isopropylidenepentofuranoses directly from D-sugars, MeOH and acetone at mild condition. The best catalyst was H-beta zeolite containing a Si/Al molar ratio of 150, where a yield of >83% was obtained. The overall yields of the five-step procedure to 1,4-dideoxy-1,4-imino-L-lyxitol and 1,4-dideoxy-1,4-imino-D-lyxitol were 57% and 50%, respectively. This synthetic procedure has several advantages such as competitive overall yield, reduced number of steps, and mild reaction conditions. Furthermore, the zeolite catalyst can be easily recovered from the reaction mixture and reused with no loss of activity.
- Fan,Chuah,Jaenicke, Stephan
-
p. 103 - 114
(2018/12/13)
-
- Preparation method of capecitabine intermediate
-
The invention discloses a preparation method of a capecitabine intermediate 1, 2, 3-O-triacetyl-5-deoxy-D-furanoside, which belongs to the technical field of medicinal chemistry. According to the invention, D-ribose (a compound I) is used as an initial raw material, and is subjected to a protective group reaction with methanol and acetone under the catalysis of solid acid, 1, 2, 3-hydroxyl is protected to obtain a compound II, then the compound II and thionyl chloride are subjected to a chlorination reaction, hydroxymethyl is changed into chloromethyl, a compound III is obtained, the compoundIII is subjected to a reduction reaction through platinum/carbon catalytic hydrogenation to obtain a compound IV, the compound IV is subjected to acidic hydrolysis to obtain a compound V, and the compound V is subjected to acetylation to obtain a target compound VI. The whole process is short in reaction step and high in economy; side reactions are few, and product purity is high; no wastewater isgenerated in the first three steps, so that the method is more environment-friendly; and the method is beneficial to industrial production of the capecitabine intermediate 1, 2, 3-O-triacetyl-5-deoxy-D-furanoside.
- -
-
Paragraph 0007; 0016-0017
(2019/12/02)
-
- Preparation process for L-lyxose
-
The invention belongs to the technical field of L-lyxose preparation, and relates in particular to a preparation process for L-lyxose. The preparation process comprises the following steps: synthesisofzing 1-methyl-D-ribose, synthesis of 2,3-propylidene-methyl-D-ribose, synthesis of 2,3-propylidene-methylsulfonyl-mthyl-D-ribose, and synthesis of 2,3-propylidene-methyl-L-lyxose and L-lyxose. Thepreparation process for the L-lyxose takes D-ribose as the raw material, and is used for synthesizing L-lyxose by methyl conversion, propylidene conversion, protective group (methylsulfonyl) conversion, and conversion de-protection, so that L-lyxose is prepared through D to L conversion and methyl and propylidene desorption. The whole preparation process is high in catalysisconversion efficiency,is relatively simple in process, adopts cheap and easily available raw materials, is simple and convenient to operate, and is safe; and the obtained product is high in purity.
- -
-
Paragraph 0024; 0027; 0031; 0034; 0038; 0041
(2019/02/25)
-
- Adenosine diphosphate ribose compound, preparation method and biological activity thereof
-
The invention discloses an adenosine diphosphate ribose compound, which has a general formula shown as (I), wherein the definitions of all substituents are detailed in the specification. In addition,the invention also discloses a preparation method and application of the compound. The adenosine diphosphate ribose (ADPR) structural analogue provided by the invention has specific TRPM2 (transient receptor potential melastatin 2) inhibitory activity.
- -
-
Paragraph 0115-0119
(2019/01/24)
-
- Selective inhibition of TRPM2 channel by two novel synthesized ADPR analogues
-
Transient receptor potential melastatin-2 (TRPM2) channel critical for monitoring internal body temperature is implicated in the pathological processes such as neurodegeneration. However, lacking selective and potent TRPM2 inhibitors impedes investigation and validation of the channel as a drug target. To discover novel and selective TRPM2 inhibitors, a series of adenosine 5′-diphosphoribose analogues were synthesized, and their activities and selectivity were evaluated. Whole-cell patch-clamp recordings were employed for screen and evaluation of synthesized compounds. Two compounds, 7i and 8a, were identified as TRPM2 inhibitors with IC50 of 5.7 and 5.4?μm, respectively. Both 7i and 8a inhibited TRPM2 current without affecting TRPM7, TRPM8, TRPV1 and TRPV3. These two TRPM2 inhibitors can serve as new pharmacological tools for further investigation and validation of TRPM2 channel as a drug target, and the summarized structure–activity relationship (SAR) may also provide insights into further improving existing inhibitors as potential lead compounds.
- Luo, Xiao,Li, Meng,Zhan, Kaiyu,Yang, Wei,Zhang, Lihe,Wang, KeWei,Yu, Peilin,Zhang, Liangren
-
p. 552 - 566
(2017/11/21)
-
- Synthesis of N-alkyl substituted iminosugars from D-ribose
-
An effective and facile method for the synthesis of N-alkylated hydroxylpyrrolidine and hydroxylpiperidine is described. A number of N-alkyl substituted iminosugars were prepared using iodine-induced intramolecular cyclization of acyclic alkenylamines as key step.
- Wang, Haibo,Pan, Yang,Tang, Qin,Zou, Wei,Shao, Huawu
-
supporting information
p. 73 - 75
(2017/10/26)
-
- In situ characterization of advanced glycation end products (AGEs) in collagen and model extracellular matrix by solid state NMR
-
Non-enzymatic glycation of extracellular matrix with (U-13C5)-d-ribose-5-phosphate (R5P), enables in situ 2D ssNMR identification of many deleterious protein modifications and crosslinks, including previously unreported oxalamido and
- Li,Rajan,Wong,Reid,Duer,Somovilla,Martinez-Saez,Bernardes,Hayward,Shanahan
-
supporting information
p. 13316 - 13319
(2017/12/26)
-
- Capecitabine and wherein the intermediate preparation method
-
The invention discloses a preparation method of capecitabine. The method comprises the following steps: based on D-ribose serving as a starting raw material, carrying out hydroxyl protection, 5-site tosylation, iodine substitution, hypophosphorous acid deiodination and acetylation so as to obtain the key intermediate 12,3-tri-O-acetyl-5-deoxy-beta-D-ribofuranose; carrying out glycosylation on the key intermediate and 5-fluorocytosine; and finally, carrying out N-4 site acylation and deprotection so as to obtain the capecitabine. In the method, a metal catalyst dose not need to be used for participating in reaction, the reaction condition is mild, and the yield is high, thus the method is economical and effective as well as suitable for industrial production on a large scale.
- -
-
Paragraph 0035; 0036; 0037
(2017/02/09)
-
- Diversity-Oriented Synthesis of cis -3,4-Dihydroxylated Piperidine and Its Higher Saturated and Unsaturated Homologues from d -Ribose and Their Glycosidase-Inhibition Study 1
-
The synthesis of six-, seven-, and eight-membered cis-dihydroxy azacycles has been accomplished from d-ribose using Vasella reductive amination as a key step and utilization of hydroboration-oxidation, Mitsunobu reaction, and ring-closing metathesis (RCM) reactions in a facile manner. These homologous dihydroxylated heterocyclic scaffolds were subjected to the glycosidase inhibition assays. However, only a moderate inhibitory activity for three out of five compounds was observed against α-glucosidases with a high degree of selectivity.
- Ajay, Sama,Arora, Inderpreet,Saidhareddy, Puli,Shaw, Arun K.
-
p. 2721 - 2725
(2016/11/30)
-
- N2-glycosyl-substituted 1,2,3-triazole compound and synthesis method and application thereof
-
The invention relates to an N2-glycosyl-substituted 1,2,3-triazole compound and a synthesis method and application thereof. The general structural formula of the N2-glycosyl-substituted 1,2,3-triazole compound is shown in the specification, wherein R1 indicates H atoms or halogen atoms or alkyl groups of 1-6 carbon atoms or alkoxy groups of 3-10 carbon atoms or aryl groups or heterocyclic groups or benzoyl groups or formyloxy groups or cyano groups, and R indicates hydrogen or alkyl groups or halogen atoms or nitro groups or alkoxy groups or cyano groups and is located at ortho-position, meta-position and para-position single substitution or polysubstitution of aromatic rings. The N2-glycosyl-substituted 1,2,3-triazole compound and the synthesis method and application thereof have the advantages that synthesis conditions are easy to control, the yield is high, and the cost is low; application of triazole derivatives in the fields of pesticide, medicine, food and the like is further promoted; a new way is provided for research and development of high-value utilization and modification of triazole; the compound has high inhibiting ability for alpha-glucosidase and can be further developed into medicine used for treating or assisting in treating diabetes mellitus type 2.
- -
-
Paragraph 0050; 0052; 0053
(2017/01/26)
-
- South (S)- and north (N)-methanocarba-7-deazaadenosine analogues as inhibitors of human adenosine kinase
-
Adenosine kinase (AdK) inhibitors raise endogenous adenosine levels, particularly in disease states, and have potential for treatment of seizures, neurodegeneration, and inflammation. On the basis of the South (S) ribose conformation and molecular dynamics (MD) analysis of nucleoside inhibitors bound in AdK X-ray crystallographic structures, (S)- and North (N)-methanocarba (bicyclo[3.1.0]hexane) derivatives of known inhibitors were prepared and compared as human (h) AdK inhibitors. 5′-Hydroxy (34, MRS4202 (S); 55, MRS4380 (N)) and 5′-deoxy 38a (MRS4203 (S)) analogues, containing 7- and N6-NH phenyl groups in 7-deazaadenine, robustly inhibited AdK activity (IC50 ~ 100 nM), while the 5′-hydroxy derivative 30 lacking the phenyl substituents was weak. Docking in the hAdK X-ray structure and MD simulation suggested a mode of binding similar to 5′-deoxy-5-iodotubercidin and other known inhibitors. Thus, a structure-based design approach for further potency enhancement is possible. The potent AdK inhibitors in this study are ready to be further tested in animal models of epilepsy.
- Toti, Kiran S.,Osborne, Danielle,Ciancetta, Antonella,Boison, Detlev,Jacobson, Kenneth A.
-
supporting information
p. 6860 - 6877
(2016/08/05)
-
- Identification of a cytotoxic molecule in heat-modified citrus pectin
-
Modified forms of citrus pectin possess anticancer properties. However, their mechanism of action and the structural features involved remain unclear. Here, we showed that citrus pectin modified by heat treatment displayed cytotoxic effects in cancer cells. A fractionation approach was used aiming to identify active molecules. Dialysis and ethanol precipitation followed by HPLC analysis evidenced that most of the activity was related to molecules with molecular weight corresponding to low degree of polymerization oligogalacturonic acid. Heat-treatment of galacturonic acid also generated cytotoxic molecules. Furthermore, heat-modified galacturonic acid and heat-fragmented pectin contained the same molecule that induced cell death when isolated by HPLC separation. Mass spectrometry analyses revealed that 4,5-dihydroxy-2-cyclopenten-1-one was one cytotoxic molecule present in heat-treated pectin. Finally, we synthesized the enantiopure (4R,5R)-4,5-dihydroxy-2-cyclopenten-1-one and demonstrated that this molecule was cytotoxic and induced a similar pattern of apoptotic-like features than heat-modified pectin.
- Leclere, Lionel,Fransolet, Maude,Cambier, Pierre,El Bkassiny, Sandy,Tikad, Abdellatif,Dieu, Marc,Vincent, Stéphane P.,Van Cutsem, Pierre,Michiels, Carine
-
-
- METHOD FOR PRODUCING THIOLANE SKELETON-TYPE GLYCOCONJUGATE, AND THIOLANE SKELETON-TYPE GLYCOCONJUGATE
-
There is provided a production method of a compound represented by the following formula (II) through a step of reacting a compound represented by the following General Formula (I) with a sulfur compound. In General Formulas (I) and (II), R1 represents a hydrogen atom or an acyl group, R2 represents a hydrogen atom, a fluorine atom, an acyloxy group, an arylmethyloxy group, an allyloxy group, an arylmethyloxycarbonyloxy group, or an allyloxycarbonyloxy group, R3 represents a hydrogen atom or an acyloxy group, R5 represents an alkyl group or an aryl group, and X represents a leaving group. Here, in a case where R2 is a fluorine atom, an acyloxy group, an arylmethyloxy group, an allyloxy group, an arylmethyloxycarbonyloxy group, or an allyloxycarbonyloxy group, R3 is an acyloxy group.
- -
-
Paragraph 0502-0505
(2016/12/26)
-
- Synthesis of Biologically Active Piperidine Metabolites of Clopidogrel: Determination of Structure and Analyte Development
-
Clopidogrel is a prodrug anticoagulant with active metabolites that irreversibly inhibit the platelet surface GPCR P2Y12 and thus inhibit platelet activation. However, gaining an understanding of patient response has been limited due to imprecise understanding of metabolite activity and stereochemistry, and a lack of acceptable analytes for quantifying in vivo metabolite formation. Methods for the production of all bioactive metabolites of clopidogrel, their stereochemical assignment, and the development of stable analytes via three conceptually orthogonal routes are disclosed. (Chemical Equation Presented).
- Shaw, Scott A.,Balasubramanian, Balu,Bonacorsi, Samuel,Cortes, Janet Caceres,Cao, Kevin,Chen, Bang-Chi,Dai, Jun,Decicco, Carl,Goswami, Animesh,Guo, Zhiwei,Hanson, Ronald,Humphreys, W. Griffith,Lam, Patrick Y. S.,Li, Wenying,Mathur, Arvind,Maxwell, Brad D.,Michaudel, Quentin,Peng, Li,Pudzianowski, Andrew,Qiu, Feng,Su, Shun,Sun, Dawn,Tymiak, Adrienne A.,Vokits, Benjamin P.,Wang, Bei,Wexler, Ruth,Wu, Dauh-Rurng,Zhang, Yingru,Zhao, Rulin,Baran, Phil S.
-
p. 7019 - 7032
(2015/07/27)
-
- Synthesis of Aminocyclopentanetriol Derivatives
-
The present invention relates to the field of organic synthesis and describes the synthesis of specific intermediates suitable for the preparation of triazolopyrimidine compounds such as ticagrelor. The present invention provides in particular a process for the preparation of a compound of formula V comprising: a) providing a compound of formula IV , and b) reducing the compound of formula IV with activated zinc in the presence of copper to give the compound of formula V.
- -
-
Paragraph 0045; 0046; 0056
(2014/01/07)
-
- Preparation of anti -vicinal amino alcohols: Asymmetric synthesis of d - Erythro -sphinganine, (+)-spisulosine, and d - Ribo -phytosphingosine
-
Two variations of the Overman rearrangement have been developed for the highly selective synthesis of anti-vicinal amino alcohol natural products. A MOM ether-directed palladium(II)-catalyzed rearrangement of an allylic trichloroacetimidate was used as the key step for the preparation of the protein kinase C inhibitor d-erythro-sphinganine and the antitumor agent (+)-spisulosine, whereas the Overman rearrangement of chiral allylic trichloroacetimidates generated by the asymmetric reduction of an α,β-unsaturated methyl ketone allowed rapid access both to d-ribo-phytosphingosine and l-arabino-phytosphingosine.
- Calder, Ewen D. D.,Zaed, Ahmed M.,Sutherland, Andrew
-
p. 7223 - 7233
(2013/08/23)
-
- SYNTHESIS OF TRIAZOLOPYRIMIDINE COMPOUNDS
-
The present invention relates to the field of organic synthesis and describes the synthesis of specific intermediates suitable for the preparation of triazolopyrimidine compounds such as ticagrelor.
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-
Page/Page column 43; 44
(2013/07/05)
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- Formal synthesis of (-)-oleocanthal by means of a SmI2-promoted intramolecular coupling of bromoalkyne with α,β-unsaturated ester
-
A novel approach to the synthesis of (-)-oleocanthal starting from d-ribose, in which a SmI2-promoted intramolecular coupling of bromoalkyne with α,β-unsaturated ester is a key step, has been developed.
- Takahashi, Kazunori,Morita, Hiroshi,Honda, Toshio
-
scheme or table
p. 3342 - 3345
(2012/07/30)
-
- Synthesis and biological evaluation of ticagrelor derivatives as novel antiplatelet agents
-
Ticagrelor (1) is the first reversible P2Y12 receptor antagonist blocking adenine diphosphate (ADP)-induced platelet aggregation with rapid onset and offset of effects. In this study, synthesis of ticagrelor and its derivatives has been accomplished in a convergent way. The compound design was based on modifications of ticagrelor and its major metabolite (33) in order to ameliorate their pharmacokinetic properties and dosing profile. The final compounds (1a-g, 35a-g) were evaluated for their inhibitory effect on ADP-induced platelet aggregation in rats. The assay results showed that some compounds (e.g., 1b, 1d, 33, 35b, 35f) exhibited comparable potency with that of ticagrelor.
- Zhang, Hao,Liu, Jun,Zhang, Luyong,Kong, Lingyi,Yao, Hequan,Sun, Hongbin
-
supporting information; experimental part
p. 3598 - 3602
(2012/07/14)
-
- Lewis acid-assisted olefin cross-metathesis reaction: An efficient approach for the synthesis of glycosidic-pyrroloquinolinone based novel building blocks of camptothecin and evaluation of their antitumor activity
-
A series of glycosidic-pyrroloquinolinone based novel building blocks of camptothecin (2a-g) were synthesized via Lewis acid-assisted olefin cross-metathesis reaction using Ti(OiPr)4 30 mol % and 10 mol % of Grubb's second generation catalyst with good to excellent yields. Most of these compounds exhibited significant growth inhibitory effects on all the tested cancer cell lines and three compounds (2c, 2d and 2e) showed potent cytotoxic activity.
- Nagarapu, Lingaiah,Gaikwad, Hanmant K.,Bantu, Rajashaker,Ganesh Kumar,Pombala, Sujitha
-
supporting information; scheme or table
p. 1287 - 1291
(2012/03/27)
-
- A new approach to cyclopentitols using CrCl2 mediated domino reaction and ring closing metathesis. the synthesis of 4a-carba-β-d- arabinofuranose and 4a-carba-β-d-lyxofuranose
-
An efficient method for the syntheses of cyclopentitols from d-ribose is described using Nozaki-Hiyama-Kishi conditions and ring closing metathesis. In this transformation ω-deoxy-ω-iodo ribofuranoside undergoes reductive elimination in the presence of CrCl2 to give the corresponding olefin-aldehyde, which was trapped by a nucleophile under the same conditions to afford the desired diolefinic species. The ring closing metathesis reaction on the diolefinic species with a Grubbs second generation catalyst produced the required carbocycles.
- Mishra, Girija Prasad,Rao, Batchu Venkateswara
-
scheme or table
p. 812 - 817
(2011/08/06)
-
- USE OF THE IRRITATING PRINCIPAL OLEOCANTHAL IN OLIVE OIL, AS WELL AS STRUCTURALLY AND FUNCTIONALLY SIMILAR COMPOUNDS
-
The invention provides oleocanthal analogs and methods of using oleocanthals in various formulations including, food additives; pharmaceuticals; cosmetics; animal repellants; and discovery tools for mammalian irritation receptor genes, gene products, alleles, splice variants, alternate transcripts and the like.
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-
Page/Page column 16
(2011/02/18)
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- PREPARATION OF CAPECITABINE
-
The present invention relates to substantially pure capecitabine and processes for the preparation thereof.
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-
Page/Page column 21; 22
(2010/06/20)
-
- HYDROXAMIC ACID DERIVATIVES
-
The disclosure includes hydroxamic compounds of Formula I: (I) wherein P, Z, and m are defined herein. Also disclosed is a method for treating a neoplastic disease or an immune disease with these compounds.
- -
-
Page/Page column 53
(2010/08/08)
-
- SUBSTITUTED NUCLEOSIDE AND NUCLEOTIDE ANALOGS
-
Disclosed herein are nucleotide analogs with protected phosphates, methods of synthesizing nucleotide analogs with protected phosphates and methods of treating diseases and/or conditions such as viral infections, cancer, and/or parasitic diseases with the nucleotide analogs with protected phosphates.
- -
-
Page/Page column 118
(2010/10/03)
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- Palladium-catalyzed coupling reactions of thioimidate N-oxides: Access to α-alkenyl- And α-aryl-functionalized cyclic nitrones
-
(Figure Presented) Surprisingly useful are thioimidate Noxides in the preparation of aryl- and vinylsubstituted cyclic ketonitrones through the Liebeskind-Srogl reaction. This novel synthetic approach appears to be efficient and have a broad scope (see scheme).
- Schleiss, Julie,Rollin, Patrick,Tatiboueet, Arnaud
-
scheme or table
p. 577 - 580
(2010/04/05)
-
- Total synthesis of the phytotoxic stagonolides A and B
-
The chemo-enzymatic and covergent synthesis of stagonolide B and the synthesis of stagonolide A, a phytotoxic 10-membered lactone have been achieved starting from d-ribose with overall yields of 25% and 8.7%, respectively. The synthesis contained simple steps in developing three centers' key intermediates, namely the enzymatic (Novozyme-435) resolution of a propargylic alcohol followed by macrolactonization and RCM.
- Prabhakar, Peddikotla,Rajaram, Singanaboina,Reddy, Dorigondla Kumar,Shekar, Vanam,Venkateswarlu, Yenamandra
-
experimental part
p. 216 - 221
(2010/05/18)
-
- USE OF THE IRRITATING PRINCIPAL OLEOCANTHAL IN OLIVE OIL, AS WELL AS STRUCTURALLY AND FUNCTIONALLY SIMILAR COMPOUNDS
-
The invention provides methods of synthesizing the purified enantiomers of oleocanthal. The invention further provides methods of using oleocanthals in various formulations including, food additives; pharmaceuticals; cosmetics; animal repellants; and discovery tools for mammalian irritation receptor genes, gene products, alleles, splice variants, alternate transcripts and the like.
- -
-
Page/Page column 15
(2009/04/24)
-
- Total synthesis of aigialomycin D using a Ramberg - Baecklund/ RCM strategy
-
The bioactive resorcylic acid lactone aigialomycin D (1) has been synthesized by a novel combination of ring-closing metathesis (RCM) and Ramberg - Baecklund reactions. This synthetic strategy enables the Cl - C2 alkene to be masked as a sulfone during formation of the macrocycle by ring closing metathesis at the C7 - C8 olefin, thus avoiding competing formation of a cyclohexene. A subsequent Ramberg-Baecklund reaction efficiently produces the C1- C2 E-alkene. This combined RCM/ Ramberg-Baecklund reaction strategy should be widely applicable to the synthesis of maerocyclic dienes.
- Baird, Lynton J.,Timmer, Mattie S. M.,Teesdale-Spittle, Paul H.,Harvey, Joanne E.
-
supporting information; experimental part
p. 2271 - 2277
(2009/08/07)
-
- Synthesis of the transfer-RNA nucleoside queuosine by using a chiral allyl azide intermediate
-
Chilled out: Chiral allyl azides are rarely used in natural product synthesis because of their tendency to undergo a [3.3] sigmatropic rearrangement (see scheme, top). In allylic cyclopentenyl azides, this rearrangement can be suppressed at just 0°C, enabling a short convergent synthesis of the hypermodified transfer-RNA nucleoside queuosine. (Chemical Equation Presented).
- Klepper, Florian,Jahn, Eva-Maria,Hickmann, Volker,Carell, Thomas
-
p. 2325 - 2327
(2008/03/11)
-
- Mild, efficient, and selective cleavage of trityl ethers with antimony trichloride
-
Selective detritylation is quite crucial in synthetic chemistry. A mild and efficient procedure for selective hydrolysis of trityl ethers in the presence of other frequently used hydroxy protecting groups: TBDPS, Bz, Bn, Ac and Ts with antimony trichloride was described and 5′-trityl uridine was detritylated smoothly too. Copyright Taylor & Francis Group, LLC.
- Wu, Qinpei,Wang, Yuan,Chen, Wei,Liu, Hua
-
p. 1361 - 1366
(2007/10/03)
-
- Synthesis and assignment of absolute configuration of (-)-oleocanthal: A potent, naturally occurring non-steroidal anti-inflammatory and anti-oxidant agent derived from extra virgin olive oils
-
(Chemical Equation Presented) Effective total syntheses and the assignment of absolute configurations of both the (+)- and (-)-enantiomers of oleocanthal 1 (a.k.a. deacetoxy ligstroside aglycon), the latter derived from extra virgin olive oils and known to be responsible for the back of the throat irritant properties of olive oils, have been achieved. The absolute and relative stereochemistry of the naturally occurring enantiomer (-)-1 proved to be 3S,4E. Both syntheses begin with D-(-)-ribose, proceed in 12 steps, and are achieved with an overall yield of 7%. Both enantiomers proved to be non-steroidal anti-inflammatory and anti-oxidant agents.
- Smith III, Amos B.,Han, Qiang,Breslin, Paul A. S.,Beauchamp, Gary K.
-
p. 5075 - 5078
(2007/10/03)
-
- A novel synthesis of noviose and its C-(4) epimer
-
An efficient and stereoselective synthetic route has been developed to both noviose and its C-(4) epimer, thus providing a platform for the investigation of the structure-activity relationships (SAR) involving the methoxy group of noviose.
- Gammon, David W.,Hunter, Roger,Wilson, Seanette
-
p. 3141 - 3144
(2007/10/03)
-
- A general synthesis of specifically deuterated nucleotides for studies of DNA and RNA
-
An efficient procedure is described for the preparation of ribonucleotides and deoxyribonucleotides with deuterium incorporated at the 1′, 4′, or 5′ position. Three intermediates-[1-2H]-D-ribose, [4-2H]-D-ribose, and [5-2H
- Chen, Bingzi,Jamieson, Elizabeth R.,Tullius, Thomas D.
-
p. 3093 - 3096
(2007/10/03)
-
- Evaluation of D-ribose as an enantiopure building block for construction of the C-ring of taxol and its congeners
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The enantiomerically pure Z vinyl iodide 20 is shown to be readily available from D-ribose via a sequence involving zinc-promoted reductive unmasking of an aldehyde and homologation with (iodomethylene)triphenylphosphorane. The vinyl anion produced by halogen-metal exchange adds from the endo direction to an enantiopure ketone prepared from D-camphor. The resulting carbinol undergoes anionic oxy-Cope rearrangement and C-methylation with complete stereocontrol to set the appropriate C-3 stereochemistry of taxol. Dihydroxylation of this intermediate brings about facile transannular hemiketalization. DIBAL-H reduction of this intermediate does not affect the hemiketal, but does reduce the acetonide regiospecifically. An unusual transannular hydride shift occurs during subsequent heating with dibutyltin oxide, as confirmed by X-ray crystallography. When transannular hemiketalization is skirted, hydroboration-oxidation of the side chain leads to an acetaldehyde which is notably prone to β-elimination. Treatment with potassium carbonate in methanol does eventuate in ring closure via an aldol addition reaction, but only after methanol has been added in Michael fashion to the α,β-unsaturated aldehyde.
- Paquette,Bailey
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p. 7849 - 7856
(2007/10/03)
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- Carbohydrate Protease Conjugates: Stabilized Proteases for Peptide Synthesis
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The synthesis of oligopeptides using stable carbohydrate protease conjugates (CPCs) was examined in acetonitrile solvent systems.CPC was used for the preparation of peptides containing histidine, phenylalanine, tyrosine, and tryptophan in the P1 position in 60-93percent yield.The CPC was used to synthesize peptides containing both hydrophilic and hydrophobic amino acids.The P2 specificity of papain for aromatic residues was utilized for the 2 + 3 coupling of Z-Tyr-Gly-OMe to H2N-Gly-Phe-Leu-OH to generate the leucine enkephalin derivative in 79percent yield.Although papain is nonspecific for the hydrolysis of N-benzyloxycarbonyl amino acid methyl esters in aqueous solution, the rates of synthesis for these derivatives with nucleophile leucine tert-butyl ester differed by nearly 2 orders of magnitude.CPC was used to prepare the aspartame precursor Z-Asp-Phe-OMe in 90percent yield.The increased stability of CPCs prepared from periodate-modified poly(2-methacrylamido-2-deoxy-D-glucose), poly(2-methacrylamido-2-deoxy-D-galactose), and poly(5-methacrylamido-5-deoxy-D-ribose), carbohydrate materials designed to increase the aldehyde concentration in aqueous solution, suggests that the stability of CPCs is directly related to the aldehyde concentration of the carbohydrate material.Periodate oxidation of poly(2-methacrylamido-2-deoxy-D-glucose) followed by covalent attachment to α-chymotrypsin gave a CPC with catalytic activity in potassium phosphate buffer at 90 deg C for 2 h.
- Wartchow, Charles A.,Wang, Peng,Bednarski, Mark D.,Callstrom, Matthew R.
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p. 2216 - 2226
(2007/10/02)
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- EFFICIENT ENANTIOSELECTIVE SYNTHESES OF CARBOCYCLIC NUCLEOSIDE AND PROSTAGLANDIN SYNTHONS
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Simple and efficient enantioselective syntheses of two hydroxylated cyclopentenones, 2 and 10, which are useful intermediates for the synthesis of various carbocyclic nucleosides and prostaglandins, directly from readily available sugars are described.
- Ali, Syed Mashhood,Ramesh, Kakarla,Borchardt, Ronald T.
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p. 1509 - 1512
(2007/10/02)
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