- A low temperature, vinylboronate ester-mediated, iterative cross-coupling approach to xanthomonadin polyenyl pigment analogues
-
Approaches to the polyene natural product xanthomonadin, an octaenyl electron-deficient bacterial photoprotective agent, and its debromo analogue, were developed. These involved the iterative cross-coupling of multiple C2-fragments, using a vinylboronate
- Madden, Katrina S.,Knowles, Jonathan P.,Whiting, Andrew
-
-
Read Online
- Gold (I/III)-Catalyzed Trifluoromethylthiolation and Trifluoromethylselenolation of Organohalides
-
The first C?SCF3/SeCF3 cross-coupling reactions using gold redox catalysis [(MeDalphos)AuCl], AgSCF3 or Me4NSeCF3, and organohalides as substrates are reported. The new methodology enables a one-stop shop synthesis of aryl/alkenyl/alkynyl trifluoromethylthio- and selenoethers with a broad substrate scope (>60 examples with up to 97 % isolated yield). The method is scalable, and its robustness is evidenced by the late-stage functionalization of various bioactive molecules, which makes this reaction an attractive alternative in the synthesis of trifluoromethylthio- and selenoethers for pharmaceutical and agrochemical research and development.
- Mudshinge, Sagar R.,Yang, Yuhao,Xu, Bo,Hammond, Gerald B.,Lu, Zhichao
-
supporting information
(2022/02/10)
-
- Compound, preparation method and application of compound in preparation of medicine for treating small cell lung cancer
-
The invention provides a compound, a preparation method thereof and an application of the compound in preparation of drugs for treating small cell lung cancer. The structural formula of the compound is shown in the specification, and the compound generates a synergistic effect on small cell lung cancer tumor cells by blocking the activity of PARP and/or XPO1 protein. Researches show that the compound provided by the invention can effectively inhibit proliferation of small cell lung cancer cells in vivo and in vitro, and can be applied to drugs for treating small cell lung cancer.
- -
-
Paragraph 0027-0030
(2021/03/13)
-
- Total Synthesis of Malacidin A by β-Hydroxyaspartic Acid Ligation-Mediated Cyclization and Absolute Structure Establishment
-
The development of novel antibiotics is critical to combating the growing emergence of drug-resistant pathogens. Malacidin A is a new member of the calcium-dependent antibiotic (CDAs) family with activity against antibiotic-resistant pathogens. Its mode of action is distinct from classical CDAs. However, the absolute structure of malacidin A has not been established. Herein, the total syntheses of malacidin A and its analogues are reported by a combination of Fmoc-based solid-phase peptide synthesis (SPPS) and β-hydroxyaspartic acid ligation-mediated peptide cyclization. The total synthesis enabled us to establish the absolute configuration of malacidin A, which is in agreement with those for natural malacidin A confirmed by advanced Marfey's analysis in our study.
- Brady, Sean F.,Chen, Sheng,Forelli, Nicholas,Li, Xuechen,Po, Kathy Hiu Laam,Shang, Zhuo,Sun, Zhenquan
-
supporting information
p. 19868 - 19872
(2020/09/02)
-
- Enantioselective Synthesis of α-Chiral Propargylic Silanes by Copper-Catalyzed 1,4-Selective Addition of Silicon Nucleophiles to Enyne-Type α,β,γ,δ-Unsaturated Acceptors
-
A copper-catalyzed deconjugative addition of silicon nucleophiles to a broad range of enyne-type α,β,γ,δ-unsaturated acceptors with high enantiocontrol is reported. The method is 1,4-selective with hardly any formation of the 1,6-adduct. The double-bond geometry is shown to be critical for achieving this chemoselectivity: exclusive 1,4-addition for E and predominant 1,6-addition for Z. By this, E-configured enynoates, enynamides, and enynones have been converted to the corresponding α-chiral propargylic silanes with excellent enantiomeric excesses.
- Mao, Wenbin,Oestreich, Martin
-
supporting information
p. 8096 - 8100
(2020/11/02)
-
- Using Nature's polyenes as templates: studies of synthetic xanthomonadin analogues and realising their potential as antioxidants
-
Two truncated analogues of the polyenyl photoprotective xanthomonadin pigments have been synthesised utilising an iterative Heck-Mizoroki (HM)/iododeboronation cross coupling approach and investigated as models of the natural product photoprotective agent
- Madden, Katrina S.,Jokhoo, Hans R. E.,Conradi, Fabian D.,Knowles, Jonathan P.,Mullineaux, Conrad W.,Whiting, Andrew
-
supporting information
p. 3752 - 3759
(2019/04/17)
-
- Gold-Catalyzed Ring Expansion of Enyne-Lactone: Generation and Transformation of 2-Oxoninonium
-
An efficient gold-catalyzed ring-expansion reaction of enyne-lactones to form 2-oxoninonium intermediates is reported. The 2-oxoninonium generated in this work could undergo further 6π electrocyclization and aromatization reaction to produce different aromatic compounds.
- Luo, Kui,Cao, Tongxiang,Jiang, Huanfeng,Chen, Lianfen,Zhu, Shifa
-
supporting information
p. 5856 - 5859
(2017/11/10)
-
- A highly practical approach to chiral homoallylic-homopropargylic amines via aza-Barbier reaction
-
The first access to chiral homoallylic-homopropargylic amine bearing two contiguous stereocenters has been well accomplished via zinc-promoted aza-Barbier reaction. N-tert-Butanesulfinyl ketimines are well-tolerated substrates, providing the tertiary amin
- Yuan, Bin-Hua,Zhang, Zhi-Cheng,Liu, Wen-Jie,Sun, Xing-Wen
-
supporting information
p. 2147 - 2151
(2016/05/02)
-
- Enantioselective Allylation of β-Haloacrylaldehydes: Formal Total Syntheses of Pteroenone and Antillatoxin
-
A comparative study of the catalytic allylations and crotylations of (E)- and (Z)-haloacrylaldehydes by Lewis bases (chiral N,N′-dioxides) and Br?nsted acids (chiral phosphoric acids) was undertaken. The reactions proceeded with high enantio- and diastereoselectivities with slightly better asymmetric induction observed in the case of N,N′-dioxide catalysis. The formed enantioenriched chiral unsaturated haloalcohols could be considered general building blocks, as they could be used in the syntheses of more complex natural products possessing substituted 1,3-diene fragments. This was exemplified by the formal total syntheses of pteronenone and antillatoxin. A comparative study of allylations and crotylations of (E)- and (Z)-haloacrylaldehydes is undertaken under Lewis base and Br?nsted acid catalysis. The reactions proceed in both cases with high enantio- and diastereoselectivities. The formed chiral unsaturated haloalcohols can be considered as general building blocks, as exemplified by the formal total syntheses of pteronenone and antillatoxin; HBPin = pinacolborane.
- Koukal, Petr,Ul?, Jan,Ne?as, David,Kotora, Martin
-
supporting information
p. 2110 - 2114
(2016/05/09)
-
- Stereoselective Total Synthesis of Atractylodemayne A, a Conjugated 2(E),8(Z),10(E)-Triene-4,6-diyne
-
The first total synthesis of the polyacetylene natural product atractylodemayne A is reported. Stereoselective construction of the conjugated 8(Z),10(E)-diene moiety was achieved through a tethered ring-closing metathesis approach, comprising a Ru-catalyz
- Schmidt, Bernd,Aud?rsch, Stephan
-
supporting information
p. 1162 - 1165
(2016/03/15)
-
- Fully substituted pyranones via quasi-heterogeneous genuinely ligand-free migita-stille coupling of iodoacrylates
-
Migita-Stille coupling of (Z)-?2-iodoacrylates with (E)-?±-stannyl allylic alcohols to furnish 5-alkylidene-4-substituted-5,6-dihydro-2H-pyran-2-ones is efficiently catalyzed by 2% Pd black in DMF, while Pd(PPh3)4 is inactive. Heterogeneous Pd released in solution is most likely responsible for the catalysis. The reaction is applicable to other substrates, without having to resort to ligands, additives, and/or solid support for Pd. The resulting pyranones can be rearranged to fully functionalized pyranones in another single step.
- Kratochv??l, Ji????,Nov??k, Zden??k,Ghavre, Mukund,Nov??kov??, Lucie,R????i??ka, Ale??,Kune??, Ji????,Pour, Milan
-
supporting information
p. 520 - 523
(2015/03/04)
-
- ANTIDIABETIC COMPOUNDS
-
Novel compounds of the structural formula (I), and the pharmaceutically acceptable salts thereof, are agonists of G-protein coupled receptor 40 (GPR40) and may be useful in the treatment, prevention and suppression of diseases mediated by the G-protein-coupled receptor 40. The compounds of the present invention may be useful in the treatment of Type 2 diabetes mellitus, and of conditions that are often associated with this disease, including obesity and lipid disorders, such as mixed or diabetic dyslipidemia, hyperlipidemia, hypercholesterolemia, and hypertriglyceridemia.
- -
-
Page/Page column 110
(2015/09/23)
-
- SYNTHETIC RETINOIDS FOR CONTROL OF CELL DIFFERENTIATION
-
The present invention relates to synthetic retinoid compounds of formula (I) and their use in the control of cell differentiation or apoptosis.
- -
-
Page/Page column 33-34
(2012/06/30)
-
- Gold-catalyzed oxidative ring expansions and ring cleavages of alkynylcyclopropanes by intermolecular reactions oxidized by diphenylsulfoxide
-
A golden opportunity: A novel gold-catalyzed oxidative ring-expansion of unactivated cyclopropylalkynes using Ph2SO has been developed (see scheme). For substrates bearing a donor group at the cyclopropane ring, preliminary results reveal a distinct cleavage of the cyclopropane unit; such a ring cleavage is further applicable to the synthesis of 2H-pyrans. L=P(tBu) 2(o-biphenyl), Tf=triflate. Copyright
- Li, Chia-Wen,Pati, Kamalkishore,Lin, Guan-You,Sohel, Shariar Md. Abu,Hung, Hsiao-Hua,Liu, Rai-Shung
-
supporting information; experimental part
p. 9891 - 9894
(2011/02/24)
-
- Synthesis of isomeric polyacetylenes based on natural hydroxy matricaria esters
-
The construction of a library of natural and related polyacetylenes using a convergent synthetic strategy based on a palladium mediated cross-coupling reaction is described. The systematic synthetic study led to all possible alkene isomers of the hydroxy matricaria esters 29-32, and the corresponding tiglates 1-4. The synthesis of many of these compounds is described for the first time.
- Garrais, Solange,Turkington, Jennifer,Goldring, William P.D.
-
experimental part
p. 8418 - 8427
(2009/12/26)
-
- PREPARATION AND UTILITY OF SUBSTITUTED ALLYLAMINES
-
Disclosed herein are substituted allylamines having structural Formula I, processes of preparation thereof, pharmaceutical compositions thereof, and the methods of their use thereof. (I)
- -
-
Page/Page column 62
(2008/12/06)
-
- Mechanistic studies on the Heck-Mizoroki cross-coupling reaction of a hindered vinylboronate ester as a key approach to developing a highly stereoselective synthesis of a C1-C7 Z,Z,E,-triene synthon for viridenomycin
-
Mechanistic studies of the Heck-Mizoroki reaction of a vinylboronate ester with electronically different (four-substituted) aryl iodides shows that electron donors accelerate the cross-coupling, demonstrating that the oxidative addition step is not rate d
- Batsanov, Andrei S.,Knowles, Jonathan P.,Whiting, Andrew
-
p. 2525 - 2532
(2008/02/02)
-
- A closer look at the hydroiodination of propiolic acid
-
The crystal structures of cis-3-iodoacrylic acid (1), trans-3-iodoacrylic acid (2), trans-3-iodoacrylic acid methyl ester (3), 3,3-diiodopropanoic acid (4), and trans-2,3-diiodoacrylic acid (5) are reported. Compounds 1 and 2 are the kinetic and thermodynamic products, respectively, of the hydroiodination of propiolic acid. Compound 4 results from addition of a second equivalent of hydroiodic acid to 1 or 2, whereas 5 results from the addition of trace elemental iodine to propiolic acid. Copyright Taylor & Francis Group, LLC.
- Donahue, James P.
-
p. 3461 - 3471
(2007/10/03)
-
- Synthesis of 5,12-DiHETE Derivative by Palladium-Catalyzed Ternary Coupling between Vinylic Halide, a Vinylic Tin Compound, and Norbornadiene
-
A racemic 5,12-DiHETE-8,9-cyclopentadiene Diels-Alder adduct was prepared by palladium-catalyzed ternary coupling between vinylic halide, a vinylic tin compound, and norbornadiene in good yields.Both the halide and tin chain were synthesized in excellent yields by three and four steps, respectively.
- Oda, Hiroshi,Kobayashi, Tohru,Kosugi, Masanori,Migita, Toshihiko
-
p. 695 - 702
(2007/10/02)
-
- Synthesis and Properties of the Valence Tautomer of cis-Iodosocyclopropanecarboxylic Acid: 4,5-Methano-1-hydroxyiodoxol-3(1H)-one
-
4,5-Methano-1-hydroxyiodoxol-3(1H)-one (4) was synthesized from propionic acid in six steps.Key reactions included Simmons-Smith cyclopropanation of cis-3-iodopropen-2-ol, followed by pyridinium dichromate oxidation to cis-iodocyclopropanecarboxylic acid.The final iodo to iodoso oxidation used either chlorination/hydrolysis or peracetic acid procedures.Compound 4 exists in the 1-hydroxyiodoxolone form, not in the "open" cis-cyclopropanecarboxylic acid form (3), as shown by its "high" pKa (7.55) and by its ability to cleave p-(nitrophenyl)diphenyl phosphate(k = 0.0044 s-1) in pH 8 aqueous micellar solution.Compound 4 disproportionates to iodo (5) and iodoxy (7) compounds in pH 8 aqueous buffer with k = 0.027 L/(M*s).Ab initio molecular orbital calculations are described which help rationalize the observed properties of 4.The reactivity of 4 (and related species) is intimately connected to the structure and bonding around the formally hypervalent iodine atom.
- Moss, Robert A.,Wilk, Boguslawa,Krogh-Jespersen, Karsten,Westbrook, John D.
-
p. 6729 - 6734
(2007/10/02)
-
- STEREOCONTROLLED SYNTHESIS OF NATURALLY-OCCURRING POLYACETYLENES CHARACTERIZED BY (E)-1-EN-3-YNE, (E)-1-EN-3,5-DIYNE, (1E,5E)-1,5-DIEN-3-YNE, AND (1E,7E)-1,7-DIEN-3,5-DIYNE MOIETIES
-
A stereocontrolled synthesis of five naturally-occurring polyacetylenes, i.e. methyl (E)-5-(2-thienyl)-2-penten-4-ynoate, 9, (E)-N-methyl-N-(2-methylpropyl)-2-decen-4,6-diynamide, 10, (E)-1-(3-methyl-2-butenoyloxy)-2-decen-4,6-diyne, 11, (2E,6E)-1-acetoxy-2,6-decadien-4-yne, 12, and (2E,8E)-1-acetoxy-2,8-decadien-4,6-diyne, 13, is reported.The flexible strategy involves palladium(0)-copper(I) catalyzed coupling reactions to construct the carbon skeleton of the target molecules and to prepare an important C5 building block, i.e. (E)-2-penten-4-yn-1-ol, 21.This compound is also an useful intermediate to lipoxins A and B.A highly diastereoselective palladium-catalyzed carbon-carbon bond forming reaction, recently developed in our laboratory, has been used in a key synthetic step to compound 12.
- Carpita, Adriano,Neri, Dario,Rossi, Renzo
-
p. 481 - 490
(2007/10/02)
-