- A concise synthesis of the pentacyclic framework of cortistatins
-
(Chemical Equation Presented) An efficient synthesis of the pentacyclic framework of cortistatins has been developed. The key strategy comprises assembly of the A- and the CD-ring fragments by Knoevenagel reaction, facile formation of the pyran ring via e
- Yamashita, Shuji,Iso, Kentaro,Hirama, Masahiro
-
-
Read Online
- A strategy towards the synthesis of plumarellide based on biosynthesis speculation, featuring a transannular 4+2 type cyclisation from a cembranoid furanoxonium ion intermediate
-
In studies towards a biomimetic synthesis of plumarellide 1, acid-catalysed rearrangement of the furanobutenolide-based acetonide 10b led to the ring system 15b in plumarellide together with the cycloheptene-based ring system 11 found in rameswaralide 4, in a combined yield of 60%. RCM of the ω-dienes 30a and 30b led to the macrocycles 38a and 38b, respectively with the Z-configuration. Treatment of the vinyl bromide/vinyl stannanes 32a and 47 under Stille conditions failed to give the macrocycles 31a and 48, respectively. Reactions of the macrocycles 38a and 38b with TFA containing water produced the 5,6,7-tricyclic compounds 56a and 56b, respectively in >90% yield, instead of the plumarellide-based ring system 52. A summary and perspective on possible pathways from the C-13 acetoxy furanocembranoid 66 and from the C13–C14 unsaturated enol ether/cyclic hemiketal 9/59 to plumarellide 1 in vivo is given.
- Li, Yi,Palframan, Matthew J.,Pattenden, Gerald,Winne, Johan M.
-
-
Read Online
- Cyclic ethers as educts for the synthesis of lepidoptra pheromones
-
ω-Iodo(trialkylsiloxy)alkanes 2 prepared by ring opening of cyclic ethers with iodotrimethylsilane, are useful starting materials for the synthesis of pheromone components. Reaction with triphenylphosphine to give the corresponding Wittig reagent and subsequent coupling with lithium (Z)-dihex-1-enylcuprate gives (Z)-alken-1-ols 5 and 7, after deprotection, in good yields. The direct coupling of 2 with alkynes failed because of competition reactions, however, the more stable ω-iodo-1-(tert-butyldimethylsiloxy)alkanes were able to undergo C,C-coupling with alkynes. The thus formed 1-(tert-butyldimethylsiloxy)-5-decyne (13c) was hydrogenated and deprotected to give (E)-5-decen-1-ol (15c).
- Poleschner,Heydenreich,Martin
-
-
Read Online
- A Copolymerized Dodecacarborane Anion as Covalently Attached Cation Exchanger in Ion-Selective Sensors
-
The traditional cation exchangers used in ion-selective electrodes and optodes are tetraphenylborate derivatives, which are generally adequate for most analytical applications but may in some cases suffer from decomposition by acid hydrolysis, oxidants, and light. Recently, halogenated dodecacarboranes were found to be improved cation exchangers in terms of lipophilicity and chemical stability. This forms the basis for the convenient covalent attachment of the cation exchanger to the polymeric backbone of the sensing material. This is a challenge that has not satisfactorily been solved and which is especially important in view of developing ultraminiaturized sensing arrays. Here, a C-derivative of the closo-dodecacarborane anion (CB11H 12-) with a polymerizable group was synthesized as a chemically stable cation exchanger. This new derivative was copolymerized with methyl methacrylate and decyl methacrylate (MMA-DMA) to fabricate a plasticizer-free polymer with cation-exchange properties. This polymer could be conveniently blended with traditional plasticized poly(vinyl chloride) or with noncrosslinked methacrylic polymers to give solvent cast films that appear to be clear and homogeneous and that could be doped with ionophores. Optode leaching experiments supported the covalent grafting of the carborane anions. Ion-selective membranes and optode thin films were evaluated in terms of response function, response time, and selectivity. In all cases, the new material exhibited behavior similar to free tetraphenylborate derivative-based membranes. As a result of these studies, an all-polymeric plasticizer-free calcium-selective membrane was fabricated on the basis of the covalently attached carborane, a recently introduced grafted calcium ionophore, and an MMA-DMA polymer matrix. The resulting ion-selective electrodes showed Nernstian response slopes and rapid response times, demonstrating that covalent grafting of all sensing components is a feasible approach to the development of ion sensors.
- Qin, Yu,Bakker, Eric
-
-
Read Online
- COMPOUNDS AS INHIBITORS OF MACROPHAGE MIGRATION INHIBITORY FACTOR
-
The present invention provides compounds of Formula (I) shown above and their pharmaceutically acceptable salt, solvates, isomers, or prodrugs, as well as pharmaceutical compositions containing these compounds. Also provided by the invention is a method for treating a disorder mediated by macrophage migration inhibitory factor in a subject, comprising administering to the subject in need thereof a compound or a pharmaceutical composition of this invention.
- -
-
Paragraph 081
(2020/09/27)
-
- Formation, Alkylation, and Hydrolysis of Chiral Nonracemic N-Amino Cyclic Carbamate Hydrazones: An Approach to the Enantioselective α-Alkylation of Ketones
-
The α-alkylation of ketones is a fundamental synthetic transformation. The development of asymmetric variants of this reaction is important given that numerous natural products, drugs, and related compounds exist as α-functionalized ketones or derivatives thereof. We previously reported our preliminary studies on the development of a new enantioselective ketone α-alkylation procedure using N-amino cyclic carbamate (ACC) auxiliaries. In comparison to other auxiliary-based methods, ACC alkylation offers a number of advantages and is both highly enantioselective and high yielding. Herein, we provide a full account of our studies on the enantioselective ACC ketone α-alkylation method.
- Huynh, Uyen,McDonald, Stacey L.,Lim, Daniel,Uddin, Md. Nasir,Wengryniuk, Sarah E.,Dey, Sumit,Coltart, Don M.
-
p. 12951 - 12964
(2018/11/30)
-
- Evolution of a Polyene Cyclization Cascade for the Total Synthesis of (?)-Cyclosmenospongine
-
We report a full account on the development of a unique cationic polyene cyclization for the total synthesis of the tetracyclic meroterpenoid (?)-cyclosmenospongine. A highly convergent three-component coupling strategy enabled rapid access to individual cyclization precursors that were tested for their reactivity. The successful transformation generates three rings and sets four consecutive stereocenters in a single operation proceeding in a highly efficient manner to give exclusively the trans-decalin framework. In addition, we found that the enol ether geometry and the relative configuration of C3 and C8 are crucial for the success of the polyene cyclization.
- Speck, Klaus,Magauer, Thomas
-
supporting information
p. 1157 - 1165
(2017/02/05)
-
- Synthesis of Macrocyclic Lactones via Ring Transformation of 4-(ω-Hydroxyalkyl)-1,3-oxazol-5(4H)-ones
-
The synthesis of α-benzamido-α-benzyl lactones 23 of various ring size was achieved either via ‘direct amide cyclization’ by treatment of 2-benzamido-2-benzyl-ω-hydroxy-N,N-dimethylalkanamides 21 in toluene at 90 – 110° with HCl gas or by ‘ring transformation’ of 4-benzyl-4-(ω-hydroxyalkyl)-2-phenyl-1,3-oxazol-5(4H)-ones under the same conditions. The precursors were obtained by C-alkylations of 4-benzyl-2-phenyl-1,3-oxazol-5(4H)-one (15) with THP- or TBDMS-protected ω-hydroxyalkyl iodides. Ring opening of the THP-protected oxazolones by treatment with Me2NH followed by deprotection of the OH group gave the diamides 21, whereas deprotection of the TBDMS series of oxazolones 25 with TBAF followed by treatment with HCl gas led to the corresponding lactones 23 in a one-pot reaction.
- Fritschi, Stephan P.,Linden, Anthony,Heimgartner, Heinz
-
p. 523 - 538
(2016/07/22)
-
- PYRIDINE DERIVATIVES AS DGAT-1 INHIBITORS
-
Described herein are compounds of formula (I): The compounds of formula (I) act as DGAT1 inhibitors and can be useful in preventing, treating or acting as a remedial agent for hyperlipidemia, diabetes mellitus and obesity.
- -
-
Page/Page column 20; 38
(2014/09/29)
-
- NOVEL ANTIVIRAL PYRROLOPYRIDINE DERIVATIVES AND METHOD FOR PREPARING THE SAME
-
The present invention relates to a pyrrolopyridine derivative represented by the Chemical Formula I, and a racemate or a stereoisomer thereof, or a pharmaceutically acceptable salt thereof, and relates to an antiviral composition including the same as an active ingredient. The compound of the Chemical Formula I has excellent antiviral activity and selectivity for wild type and resistant HIV-1, and thereby is useful as a therapeutic agent for acquired immune deficiency syndrome (AIDS).
- -
-
Paragraph 0234
(2014/09/16)
-
- NOVEL ANTIVIRAL PYRROLOPYRIDINE DERIVATIVE AND A PRODUCTION METHOD FOR SAME
-
The present invention relates to a pyrrolopyridine derivative represented by the Chemical Formula I, and a racemate or a stereoisomer thereof, or a pharmaceutically acceptable salt thereof, and relates to an antiviral composition including the same as an active ingredient. The compound of the Chemical Formula I has excellent antiviral activity and selectivity for wild type and resistant HIV-1, and thereby is useful as a therapeutic agent for acquired immune deficiency syndrome (AIDS).
- -
-
Paragraph 0232
(2014/12/09)
-
- Total synthesis of (-)-Lepistine
-
The first total synthesis of (-)-lepistine has been accomplished in 11 steps from (S)-glycidol. The synthesis features construction of the 10-membered ring via an intramolecular epoxide opening by nosylamide, regioselective dehydration to form an enol eth
- Kitabayashi, Yusuke,Yokoshima, Satoshi,Fukuyama, Tohru
-
supporting information
p. 2862 - 2864
(2014/06/23)
-
- METHODS FOR PRODUCING BIOCOMPATIBLE MATERIALS
-
A method for producing polymerisable solution which comprises dissolving an ethylenically unsaturated zwitterionic monomer in a co-monomer system comprising a functionalised ethylenically unsaturated monomer in which the zwitterionic monomer is soluble, a siloxane group-containing monomer or macromer, and a crosslinking agent is disclosed. The polymerisable solution is biocompatible and can be used to produce polymers and articles such as contact lenses.
- -
-
Page/Page column
(2013/03/26)
-
- BIOCOMPATIBLE MATERIAL
-
Monomers of formula (I) which include a vinyl group, polymers and articles, such as contact lenses, made therefrom, all of which are biocompatible, are described.
- -
-
Paragraph 0311; 0312; 0313
(2013/03/26)
-
- FUSED CYCLOPENTYL ANTAGONISTS OF CCR2
-
The present invention comprises compounds of Formula (I). wherein: R0, R1, R2, R3, R4, R5, and A are as defined in the specification. The invention also comprises a method of preventing, treating or ameliorating a syndrome, disorder or disease, wherein said syndrome, disorder or disease is type II diabetes, obesity and asthma. The invention also comprises a method of inhibiting CCR2 activity in a mammal by administration of a therapeutically effective amount of at least one compound of Formula (I)
- -
-
Page/Page column 83
(2013/10/22)
-
- Total synthesis of cortistatins A and J
-
This paper describes the details of our synthetic studies on the marine steroidal alkaloids cortistatins A and J. The key features of our strategy include (i) an efficient Knoevenagel/electrocyclic strategy to couple the diketone and the CD-ring fragment, (ii) a chemoselective radical cyclization to construct the oxabicyclo[3.2.1]octene B-ring system, (iii) a highly stereocontrolled installation of the isoquinoline unit, and (iv) a late-stage functionalization of the A-ring.
- Yamashita, Shuji,Iso, Kentaro,Kitajima, Kazuki,Himuro, Masafumi,Hirama, Masahiro
-
experimental part
p. 2408 - 2425
(2011/06/20)
-
- FUSED PYRIDAZINE DERIVATIVE COMPOUNDS AND DRUGS CONTAINING THE COMPOUNDS AS THE ACTIVE INGREDIENT
-
Fused pyridazine derivatives represented by formula (I) or pharmaceutically acceptable salts thereof (wherein each symbol has the meaning as defined in the specification.). Because of inhibiting poly(ADP-ribose)polymerase, the compounds represented by formula (I) are useful as preventives and/or remedies for various ischemic diseases (in brain, cord, heart, digestive tract, skeletal muscle, retina, etc.), inflammatory diseases (inflammatory bowel disease, multiple cerebrosclerosis, arthritis, etc.), neurodegenerative diseases (extrapyramidal disorder, Alzheimer's disease, muscular dystrophy, lumbar spinal canal stenosis, etc.), diabetes, shock, head trauma, renal failure, hyperalgesia, etc. Moreover, these compounds are useful as agents against retroviruses (HIV etc.), sensitizers in treating cancer and immunosuppressants.
- -
-
-
- Design and synthesis of multifunctional thiacalixarenes and related metal derivatives for the preparation of sol-gel hybrid materials with non-linear optical properties
-
Thiacalixarenes bearing phenylazo or ethynylic groups on the lower rims were prepared and fully characterized. The functional groups were chosen for their ability to increase the electron delocalisation over the molecule and to form metal complexes. The f
- Desroches, Cedric,Lopes, Cesar,Kessler, Vadim,Parola, Stephane
-
p. 2085 - 2092
(2007/10/03)
-
- SUBSTITUTED 4-(1H-BENZIMIDAZOL-2-YL)[1,4]DIAZEPANES USEFUL FOR THE TREATMENT ALLERGIC DISEASES
-
The present invention relates to novel 4-(1H-benzimidazol-2-yl)[1,4] diazepane derivatives of formula (1): and stereoisomers thereof, and pharmaceutically acceptable salts thereof which are useful as histamine receptor antagonists and tachykinin receptor antagonist. Such antagonists are useful in the treatment of allergic rhinitis, including seasonal rhinitis and sinusitis; inflammatory bowel diseases, including Crohn's disease and ulcerative colitis; asthma; bronchitis; and emesis.
- -
-
-
- Carboxy substituted acylic carboxamide derivatives
-
The present invention relates to novel carboxy substituted acyclic carboxamide derivatives of formula (1)): STR1and stereoisomers and pharmaceutically acceptable salts thereof and their use as tachykinin receptor antagonists. Such antagonists are useful in the treatment of tachykinin-mediated diseases and conditions disclosed herein including: asthma, cough, and bronchitis.
- -
-
-
- Novel substituted 4-(1H-benzimidazol-2-yl) [1,4]diazepanes useful for the treatment of allergic diseases
-
The present invention relates to novel 4-(1H-benzimidazol-2-yl)[1,4]diazepane derivatives of formula and stereoisomers thereof, and pharmaceutically acceptable salts thereof which are useful as histamine receptor antagonists and tachykinin receptor antagonist. Such antagonists are useful in the treatment of allergic rhinitis, including seasonal rhinitis and sinusitis; inflammatory bowel diseases, including Crohn's disease and ulcerative colitis; asthma; bronchitis; and emesis.
- -
-
-
- Substituted 4-(1H-benzimidazol-2-yl)[1,4]diazepanes useful for the treatment of allergic disease
-
The present invention relates to novel 4-(1H-benzimidazol-2-yl)[1,4]diazepane derivatives of formula (1): and stereoisomers thereof, and pharmaceutically acceptable salts thereof which are useful as histamine receptor antagonists and tachykinin receptor antagonist. Such antagonists are useful in the treatment of allergic rhinitis, including seasonal rhinitis and sinusitis; inflammatory bowel diseases, including Crohn's disease and ulcerative colitis; asthma; bronchitis; and emesis.
- -
-
-
- A highly enantioselective and diastereoselective synthesis of cyclobutanes via boronic esters
-
(equation presented) Deprotonation of enantiopure (R,R)-1,2-dicyclohexyl-1,2-ethanediol 1-chloro-4-cyanobutylboronates 5 with LDA followed by treatment with anhydrous magnesium bromide yields (R)-(trans-2-cyanocyclobutyl)boronic esters 7 in high diastereomeric and enantiomeric purity. No cyclobutane formation has been observed in the absence of at least a catalytic amount of magnesium halide.
- Man, Hon-Wah,Hiscox, William C.,Matteson, Donald S.
-
p. 379 - 381
(2008/02/11)
-
- INHIBITORS OF FARNESYL-PROTEIN TRANSFERASE
-
The present invention is directed to compounds which inhibit farnesyl-protein transferase (FTase) and the farnesylation of the oncogene protein Ras. The invention is further directed to chemotherapeutic compositions containing the compounds of this invention and methods for inhibiting farnesyl-protein transferase and the farnesylation of the oncogene protein Ras.
- -
-
-
- RHODIUM CARBENOID MEDIATED CYCLISATIONS. PART 2. SYNTHESIS OF CYCLIC ETHERS
-
Alkylation of the dianion of methyl acetoacetate with the t-butyldimethylsilyl protected α,ω-halogeno alcohols (1)-(9) gives the β-keto esters (1) which are converted into the diazo alcohols (3) by diazo transfer and desilylation.Rhodium carbenoid cyclisa
- Heslin, Julie C.,Moody, Christopher J.
-
p. 1417 - 1424
(2007/10/02)
-