• Title/Summary/Keyword: cyclization

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2-(Multimethoxyphenyl)-4-methylene-1,3-dioxolane: (III) Polymerization of 2-(2,4-Dimethoxyphenyl)-4-methylene-1,3-dioxolane with Various Cationic Catalysts

  • 장원철;배장순;공명선
    • Bulletin of the Korean Chemical Society
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    • v.20 no.12
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    • pp.1433-1436
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    • 1999
  • The 2-(2,4-dimethoxyphenyl)-4-MDO (2) underwent polymerization with ring opening as well as cyclization reaction in the presence of various cationic catalysts such as boron trifluoride, trifluoromethanesulfonic acid, p-toluenesulfonic acid, hydrochloric acid and trifluoroacetic acid. They afforded a mixture of the ring-opened poly(keto ether) and 3(2H)-dihydrofuranone derivative. Both the methylene group and oxygen atom of 1,3-dioxolane ring were participated in the reaction with cationic catalyst. The contents of the polymer and cyclization product were variable according to the acid strength of the cationic catalysts.

Approach to the Total Synthesis of Acanthoside-D

  • Ngoc, Thyen-Truong;Park, Hae-Il
    • Proceedings of the PSK Conference
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    • 2003.10b
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    • pp.186.4-187
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    • 2003
  • Acanthoside-D, one of major components of Acanthopanacis Cortex, is known as a ginseng-like substance. it has been known to possess diverse biological effects. Acanthoside-D has a furofuran lignan structure and the synthesis of which poses interesting and often unsolved proplems of stereocontrol. Although a few interesting syntheses providing this natural product have been reported, an intermolecular McMurry coupling - intramolecular Mitsunobu cyclization route has not yet been explored. We report here a short and efficient synthetic pathway to the total synthesis of Acanthoside-D from aryl aldehydes and methyl acrylates via Baylis-Hillman reaction, intermolecular McMurry coupling and intramolecular Mitsunobu cyclization as key reaction.

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Synthesis of Novel 3-Aminohydantoinyl-1.2-benzothiazine Derivatives for the COX-2 inhibitors

  • Park, Myung-Sook;Lee, Myung-Sook;Shin, Hae-Soon;Kwon, Soon-Kyoung
    • Proceedings of the PSK Conference
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    • 2002.10a
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    • pp.344.1-344.1
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    • 2002
  • We report the synthesis of several new 3-aminohydantoinyl-1.2-benzothiazine derivatives and propose an another mechanism of the cyclization to the hydantoins for the development candidates of COX-2 inhibitors. 3-Aminohydantoins 3a-d were prepared through cyclization of the condensation products that were formed by heating amino acids and tert-bytyl carbazate in quinoline according to the method of Lalezari. (omitted)

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Comparison of Catalyzing Properties of Bacterial 4-α-Glucanotransferases Focusing on Their Cyclizing Activity

  • Kim, Jung-Eun;Tran, Phuong Lan;Ko, Jae-Min;Kim, Sa-Rang;Kim, Jae-Han;Park, Jong-Tae
    • Journal of Microbiology and Biotechnology
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    • v.31 no.1
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    • pp.43-50
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    • 2021
  • A newly cloned 4-α-glucanotransferase (αGT) from Deinococcus geothermalis and two typical bacterial αGTs from Thermus scotoductus and Escherichia coli (MalQ) were investigated. Among 4 types of catalysis, the cyclization activity of αGTs that produces cycloamylose (CA), a valuable carbohydrate making inclusion complexes, was intensively studied. The new αGT, DgαGT, showed close protein sequence to the αGT from T. scotoductus (TsαGT). MalQ was clearly separated from the other two αGTs in the phylogenetic and the conserved regions analyses. The reaction velocities of disproportionation, cyclization, coupling, and hydrolysis of three αGTs were determined. Intriguingly, MalQ exhibited more than 100-fold lower cyclization activity than the others. To lesser extent, the disproportionation activity of MalQ was relatively low. DgαGT and TsαGT showed similar kinetics results, but TsαGT had nearly 10-fold lower hydrolysis activity than DgαGT. Due to the very low cyclizing activity of MalQ, DgαGT and TsαGT were selected for further analyses. When amylose was treated with DgαGT or TsαGT, CA with a broad DP range was generated immediately. The DP distribution of CA had a bimodal shape (DP 7 and 27 as peaks) for the both enzymes, but larger DPs of CA quickly decreased in the DgαGT. Cyclomaltopentaose, a rare cyclic sugar, was produced at early reaction stage and accumulated as the reactions went on in the both enzymes, but the increase was more profound in the TsαGT. Taken together, we clearly demonstrated the catalytic differences between αGT groups from thermophilic and pathogenic bacteria that and showed that αGTs play different roles depending on their lifestyle.

Synthesis of 2,5-Disubstituted Pyrrolidines from N-Alkenyl and Alkynyl N-Benzoyloxysulfonamides Catalyzed by (CuOTf)2・C6H6

  • Liu, Wei-Min;Liu, Zhen-Hong;Cheong, Wei-Wen;Priscilla, Lu-Yi Teo;Li, Yongxin;Narasaka, Koichi
    • Bulletin of the Korean Chemical Society
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    • v.31 no.3
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    • pp.563-569
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    • 2010
  • A new synthetic method of 2,5-disubstituted pyrrolidines is developed by the cyclization of unsaturated N-benzoyloxysulfonamides by $(CuOTf)_2{\cdot}C_6H_6$ in refluxing dichloroethane. Various N-4- and N-5-alkenyl and alkynyl N-benzoyloxysulfonamides are cyclized to give pyrrolidines. The cyclization proceeds via addition of sulfonamidoyl radicals to intramolecular unsaturated bonds or allylic hydrogen abstraction with the radical intermediates.

Expression of Bacillus macerans Cyclodextrin Glucanotransferase on the Cell Surface of Saccharomyces cerevisiae.

  • Kim, Gyu-Yong;Kim, Myeong-Dong;Han, Nam-Su;Seo, Jin-Ho
    • 한국생물공학회:학술대회논문집
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    • 2000.11a
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    • pp.191-193
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    • 2000
  • A whole-cell biocatalyst was constructed by immobilizing an enzyme on the surface of the yeast Saccharomyces cerevisiae. The gene encoding Bacillus macerans cyclodextrin glucanotransferase(CGTase) was fused with the AGA2 gene encoding a small peptide disulfide-linked to the aga1, a cell wall protein of a-agglutinin. The plasmid was introduced S. cerevisiae and expressed in the medium consisting of 10g/L yeast extract, 20g/L peptone, and 20g/L galactose. The activity was detected with the formation of cyclodextrin(CD) from 10g/L soluble starch. Surface display of CGTase was also verified with the halo-test, flow cytometry, and immunofluorescence microscopy. The recombinant S. cerevisiae produced ${\alpha}-cyclodextrin$ more efficiently than the free CGTase by simultaneous fermentation and cyclization as yeast consumes glucose and maltose which are inhibitors for CD synthesis.

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Syntheses of New Film-Forming Aromatic Poly(amide-imide)s Containing Isoindoloquinazolinedione Unit in the Backbone: Poly(biphenylphthalicdianhydride-oxydianiline-4,4-diamino-3-carbamoyl-benzanilide) (Poly(BPDA-ODA-DACB))

  • Kang, Seog-Joo;Hong, Sung-Il;Park, Chong-Rae;Oh, Tae-Jin
    • Fibers and Polymers
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    • v.2 no.2
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    • pp.92-97
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    • 2001
  • New film forming aromatic poly(amide-imide)s containing isoindoloquinazolinedione (IQ) unit in the backbone chain (polymer XIV) have been successfully synthesized by preparing prepolymers of poly(amic acid-carbonamide). followed by subsequent thermal cyclization of the prepolymers. 4,4-Diamino-3-carbamoylbenzanilide (DACB) V has been synthesized by reduction of 3-carbamoyl-4-amino-4-nitrobenzanilide IV. The prepolymers of poly(amic-acid-carbonamide) (polymers VII and VIII) which exhibit viscosities ranging from 1.4 to 1.7 dl/g have been prepared by a condensation polymerization of monomers such as BPDA, ODA, and DACB. Polymer XIV has been obtained by thermal cyclization of the polymers VII and VIII. During the thermal cyclization reaction, imide ring structure was first introduced and then transformed to the structure of IQ unit. The thermal degradation rate of the resultant polymers were influenced by the cleavage of amide bond but the final char yield was comparable to that of poly(BPDA-ODA).

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Protein Cyclization Enhanced Thermostability and Exopeptidase-Resistance of Green Fluorescent Protein

  • Zhao, Zhonglin;Ma, Xin;Li, Liang;Zhang, Wei;Ping, Shuzhen;Xu, Ming-Qun;Lin, Min
    • Journal of Microbiology and Biotechnology
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    • v.20 no.3
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    • pp.460-466
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    • 2010
  • A mutant of green fluorescent protein ($GFPmut3^*$) from the jellyfish Aequorea victoria was cyclized in vitro and in vivo by the use of a naturally split intein from the dnaE gene of Synechocystis species PCC6803 (Ssp). Cyclization of $GFPmut3^*$ was confirmed by amino acid sequencing and resulted in an increased electrophoretic mobility compared with the linear $GFPmut3^*$. The circular $GFPmut3^*$ was $5^{\circ}C$ more thermostable than the linear form and significantly more resistant to proteolysis of exopeptidase. The circular $GFPmut3^*$ also displayed increased relative fluorescence intensity. In addition, chemical stability of $GFPmut3^*$ against GdnHCl revealed more stability of the circular form compared with the linear form.

Mutant cAMP Receptor Protein Binds to DNA without DNA Bending (DNA 벤딩(휨) 없이 돌연변이 cAMP 수용체 단백질의 결합)

  • Gang, Jong-Back
    • Journal of Life Science
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    • v.16 no.7 s.80
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    • pp.1225-1228
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    • 2006
  • Cyclic AMP receptor protein (CRP) complexed with cAMP binds to DNA and induces sharp DNA bending around ${\sim}90$ degree. Previous publication (5), however, reported that mutant CRP:cGMP complex showed high migration rate relative to mutant CRP:cAMP complex on native polyacrylamide gel. To confirm DNA structural change in the presence of CRP and cyclic nucleotide, molar cyclization factor $(j_M)$ [13] was measured with 6 constructed DNA fragments. Nonlinear regression analysis of $j_M$ data indicated that mutant CRP did not induce DNA bending in the presence of cGMP but bent DNA in the presence of cAMP without any helical twist change in DNA.

New Radiolytic Cyclization Products, Phlorocyclin and Isophlorocyclin Exhibit Anti-inflammatory Effects in LPS-stimulated Macrophages

  • Tae Hoon Kim
    • Journal of Radiation Industry
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    • v.18 no.1
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    • pp.63-70
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    • 2024
  • Phlorocyclin (PC) and isophorocyclin (IPC) are rare benzofuran derivaitves obtained from the representive dihydrochalcone glucoside, phloridzin (PZ) and are a type of neolignan backbone with a potential anti-glycative agents. However, research related to the enhancement of biological functionallites to inflammation of the newly converted products is very limited. This research was directed with the purpose of discovery more effective anti-inflammatory agents in macrophages of newly radiolysis products PC and IPC. The anti-inflammatory capacities of the characterized products in RAW 264.7 and DH82 macrophages treated with lipopolysaccharide (LPS) to stimulate an inflammation response were examined. The pro-inflammatory factors such as prostaglandin E2 (PGE2), tumor necrosis factor-α (TNF-α), nitric oxide (NO), interleukin-6 (IL-6), and IL-10, without cytotoxicity in LPS-stimulated macrophages, were significantly inhibited after treatment with PC and IPC, when compared to PZ. Moreover, PC and IPC decreased the appearance of cyclooxygenase-2 (COX-2) and inducible NO synthase (iNOS) proteins in macrophages. The cyclization products modified by radiolysis showed the greatest anti-inflammatory effects in macrophage cells, indicating PC and IPC are a potential candidate for use in anti-inflammatory agents.