| 词条 | Quinone methide |
| 释义 |
A quinone methide is a type of conjugated organic compound that contain a cyclohexadiene with a carbonyl and an exocyclic methylene group or extended alkene unit. It is analogous to a quinone, but having one of the double bonded oxygens replaced with a carbon. The carbonyl and methylene are usually oriented either ortho or para to each other. There are some examples of transient synthetic meta quinone methides. A quinone dimethide is a related derivative in which both carbonyl groups of a quinone are replaced by methylene groups. A well studied example is tetracyanoquinodimethane. PropertiesQuinone methides are more polar than quinones, and therefore more chemically reactive in a variety of situations. Simple quinone methides are short lived reactive intermediates that are not stable enough to be isolated under normal circumstances but quickly react with nucleophiles and other reactants. Some quinone methides have structural (e.g. steric hindrance) or electronic characteristics that stabilize them enough to be isolated. Occurrence and applicationsQuinones methides and their derivatives are common constituents of biological systems. Quinone methanide itself arises by the degradation of tyrosine, leading ultimately to p-cresol.[1] Various quinone methides are directly involved in the process of lignification (creation of complex lignin polymers) in plants.[2] Many quinone methides show pronounced biological activity. They have been implicated as the ultimate cytotoxins responsible for the effects of such agents as antitumor drugs, antibiotics, and DNA alkylators.[3] Oxidation to a reactive quinone methide is the mechanistic basis of many phenolic anti-cancer drugs. {{multiple image|align = right |total_width= 400 |image1= Celastrol.png |width1= 1109 |height1= 798 |image2= Pristimerin.png |width2= 1185 |height2= 799 }} Celastrol is a triterpenoid quinone methide isolated from Tripterygium wilfordii (Thunder of God vine) and Celastrus regelii that exhibits antioxidant (15 times the potency of α-tocopherol),[4] anti-inflammatory,[5] anticancer,[6][7][8][9] and insecticidal [10] activities. Pristimerin, the methyl ester of celasterol, is a triterpenoid quinone methide isolated from Maytenus heterophylla that displays antitumor and antiviral [11] activities. Pristimerin has also been found to have a contraceptive effect due to its inhibiting effect on the calcium channel of sperm (CatSper).[12] {{-}}{{multiple image|align = left |image1= Taxodone-to-taxodione.png |width1= 400 |image2= Maytenoquinone.png |width2= 150 |caption2= Maytenoquinone }} Taxodone and its oxidized rearrangement product, taxodione, are diterpenoid quinone methides found in Taxodium distichum (bald cypress), Rosmarinus officinalis (rosemary), several Salvia species and other plants, that display anticancer,[13][14][15] antibacterial,[16][17][18] antioxidant,[19] antifungal,[20] insecticide,[21] and antifeedant [22] activities. Maytenoquinone, an isomer of taxodione, is a biologically active quinone methide found in Maytenus dispermus.[23] {{-}}Kendomycin is an antitumor antibacterial quinone methide macrolide first isolated from the bacterium Streptomyces violaceoruber.[24] It has potent activity as an endothelin receptor antagonist and anti-osteoporosis agent.[25]Elansolid A3 is a quinone methide from the bacterium Chitinophaga sancti that displays antibiotic activity.[26] Antibacterial quinone methides, 20-epi-isoiguesterinol, 6-oxoisoiguesterin, isoiguesterin and isoiguesterinol were found in Salacia madagascariensis.[27] Quinone methides tingenone and netzahualcoyonol were isolated from Salacia petenensis.[28] Nortriterpenoid quinone methide amazoquinone and (7S, 8S)-7-hydroxy-7,8-dihydro-tingenone were isolated from Maytenus amazonica.[29] An antimicrobrial quinone methide, 15 alpha-hydroxypristimerin, was isolated from a South American medicinal plant, Maytenus scutioides.[30] PreparationQuinone methides are often prepared by oxidation of the corresponding ortho or para phenol toluene. Quinone methides can be produced in aqueous solution by photochemical dehydration of o-hydroxybenzyl alcohols. ReactionsQuinone methides are electrophilic Michael acceptors that generally react quickly with nucleophiles, other reactants, and are readily reduced. Quinone methides are conjugated but not aromatic. Conjugate addition usually breaks the conjugation. Reduction can either rearomatise the compound or break the conjugation. References1. ^Stich, T. A.; Myers, W. K.; Britt, R. D., "Paramagnetic intermediates generated by radical S-adenosylmethionine (SAM) enzymes", Acc. Chem. Res. 2014, 47, 2235-2243. 2. ^Quinone Methides in Lignification 3. ^{{cite journal |vauthors=Wang P, Song Y, Zhang L, He H, Zhou X | title = Quinone methide derivatives: important intermediates to DNA alkylating and DNA cross-linking actions | journal = Curr Med Chem | year = 2005 | volume = 12 | issue = 24 | pages = 2893–2913 | pmid = 16305478 | doi=10.2174/092986705774454724}} 4. ^{{cite journal |vauthors=Allison AC, Cacabelos R, Lombardi VR, Alvarez XA, Vigo C | title = Celastrol, a potent antioxidant and anti-inflammatory drug, as a possible treatment for Alzheimer's disease.| journal = Prog Neuropsychopharmacol Biol Psychiatry | year = 2001 | volume = 25 | issue = 7 | pages = 1341–1357 | doi=10.1016/S0278-5846(01)00192-0 | pmid=11513350}} 5. ^{{cite journal |vauthors=Kim DH, Shin EK, Kim YH, Lee BW, Jun JG, Park JH, Kim JK | title = Suppression of inflammatory responses by celastrol, a quinone methide triterpenoid isolated from Celastrus regelii | journal = Eur J Clin Invest | year = 2009 | volume = 39 | issue = 9 | pages = 819–827 | doi=10.1111/j.1365-2362.2009.02186.x | pmid=19549173}} 6. ^{{cite journal |vauthors=Lee JH, Choi KJ, Seo WD, Jang SY, Kim M, Lee BW, Kim JY, Kang S, Park KH, Lee YS, Bae S | title = Enhancement of radiation sensitivity in lung cancer cells by celastrol is mediated by inhibition of Hsp90.| journal = Int J Mol Med| year = 2011 | volume = 27 | issue = 3 | pages = 441–446 | pmid = 21249311 | doi=10.3892/ijmm.2011.601}} 7. ^{{cite journal | author = Tiedemann| title = Identification of a potent natural triterpenoid inhibitor of proteosome chymotrypsin-like activity and NF-kappaB with antimyeloma activity in vitro and in vivo. | journal = Blood | year = 2009 | volume = 113 | pages = 4027–37 | doi=10.1182/blood-2008-09-179796 | pmid=19096011 | issue=17|display-authors=etal | pmc=3952546}} 8. ^{{cite journal |vauthors=Zhu H, Liu XW, Cai TY, Cao J, Tu CX, Lu W, He QJ, Yang B | title = Celastrol acts as a potent antimetastatic agent targeting beta1 integrin and inhibiting cell-extracellular matrix adhesion, in part via the p38 mitogen-activated protein kinase pathway | journal = J Pharmacol Exp Ther | year = 2010 | volume = 334 | issue = 2 | pages = 489–499 | pmid = 20472666 | doi=10.1124/jpet.110.165654}} 9. ^{{cite journal | author = Byun| title = Reactive oxygen species-dependent activation of Bax and Poly(ADP)-ribose) polymerase-1 is required for mitochondrial cell death induced by triterpenoid Pristimerin in human cervical cancer cells. | journal = Mol. Pharmacol. | year = 2009 | volume = 76 | pages = 734–44 | doi=10.1124/mol.109.056259 | pmid=19574249 | issue=4|display-authors=etal}} 10. ^{{cite journal |vauthors=Avilla J, Teixidò A, Velázquez C, Alvarenga N, Ferro E, Canela R | title = Insecticidal activity of Maytenus species (Celastraceae) nortriterpene quinone methides against codling moth, Cydia pomonella (L.) (Lepidoptera: tortricidae).| journal = Journal of Agricultural and Food Chemistry | year = 2000 | volume = 48 | issue = 1 | pages = 88–92 | doi=10.1021/jf990008w | pmid=10637057}} 11. ^{{cite journal |vauthors=Murayama T, Eizuru Y, Yamada R, Sadanari H, Matsubara K, Rukung G, Tolo FM, Mungai GM, Kofi-Tsekpo M | title = Anticytomegalovirus activity of pristimerin, a triterpenoid quinone methide isolated from Maytenus heterophylla (Eckl. & Zeyh.).| journal = Antivir Chem Chemother | year = 2007 | volume = 18 | issue = 3 | pages = 133–139| pmid = 17626597 | doi=10.1177/095632020701800303}} 12. ^{{cite journal |authors=Nadja Mannowetza, Melissa R. Millera, and Polina V. Lishko | title = Regulation of the sperm calcium channel CatSper by endogenous steroids and plant triterpenoids| journal = Proceedings of the National Academy of Sciences of the United States of America | year = 2017 | volume = 114| issue = 22| pages = 5743–5748| doi=10.1073/pnas.1700367114 | pmid = 28507119| pmc = 5465908}} 13. ^{{cite journal |author1=Kupchan, S. M. |author2=Karim, A |author3=Marcks, C. | title = Tumor inhibitors. XXXIV. Taxodione and taxodone, two novel diterpenoid quinone methide tumor inhibitors from Taxodium distichum| journal = J Am Chem Soc | year = 1968| volume = 90 | pages = 5923 | issue = 21 | doi = 10.1021/ja01023a061 }} 14. ^{{cite journal |vauthors=Zaghloul AM, Gohar AA, Naiem ZA, Abdel Bar FM | title = Taxodione, a DNA-binding compound from Taxodium distichum L. (Rich.). | journal = Z Naturforsch C | year = 2008| volume = 63 | issue = 5–6| pages = 355–360 | doi=10.1515/znc-2008-5-608}} 15. ^{{cite journal | author = Ayhan Ulubelen, Gülaçti Topçu, Hee-Byung Chai and John M. Pezzuto | title = Cytotoxic Activity of Diterpenoids Isolated from Salvia hypargeia | journal = Pharmaceutical Biology | year = 1999| volume = 37 | issue = 2 | pages = 148–151 | doi=10.1076/phbi.37.2.148.6082}} 16. ^{{cite journal |author1=Vivek K. Bajpai |author2=Sun Chul Kan |lastauthoramp=yes | title = Antibacterial abietane-type diterpenoid, taxodone from Metasequoia glyptostroboides Miki ex Hu| journal = Journal of Biosciences | year = 2010| volume = 35| pages = 533–538| issue = 4 | doi=10.1007/s12038-010-0061-z}} 17. ^{{cite journal |author1=Vivek K. Bajpai |author2=Minkyun Na |author3=Sun Chul Kang | title = The role of bioactive substances in controlling foodborne pathogens derived from Metasequoia glyptostroboides Miki ex Hu| journal = Food and Chemical Toxicology | year = 2010| volume = 48|issue=7 | pages = 1945–1949 | doi=10.1016/j.fct.2010.04.041}} 18. ^{{cite journal |vauthors=Tada M, Kurabe J, Yoshida T, Ohkanda T, Matsumoto Y | title = Syntheses and antibacterial activities of diterpene catechol derivatives with abietane, totarane and podocarpane skeletons against methicillin-resistant Staphylococcus aureus and Propionibacterium acnes | journal = Chem Pharm Bull | year = 2010| volume = 58 | issue = 6 | pages = 818–824 | doi=10.1248/cpb.58.818}} 19. ^{{cite journal |author1=Ufuk Kolak |author2=Ahmed Kabouche |author3=Mehmet Öztürk |author4=Zahia Kabouche |author5=Gülaçtl Topçu |author6=Ayhan Ulubelen |authorlink6=Ayhan Ulubelen | title = Antioxidant diterpenoids from the roots of Salvia barrelieri| journal = Phytochemical Analysis | year = 2009| volume = 20| pages = 320–327| issue = 4 | doi=10.1002/pca.1130}} 20. ^{{cite journal |author1=Norihisa Kusumoto |author2=Tatsuya Ashitani |author3=Tetsuya Murayama |author4=Koichi Ogiyama |author5=Koetsu Takahashi | title = Antifungal Abietane-Type Diterpenes from the Cones of Taxodium distichum Rich| journal = Journal of Chemical Ecology | year = 2010| volume = 36| pages = 1381–1386| issue = 12 | doi=10.1007/s10886-010-9875-2|pmid=21072573 }} 21. ^{{cite journal |author1=Norihisa Kusumoto |author2=Tatsuya Ashitani |author3=Yuichi Hayasaka |author4=Tetsuya Murayama |author5=Koichi Ogiyama |author6=Koetsu Takahashi | title = Antitermitic Activities of Abietane-type Diterpenes from Taxodium distichum Cones| journal = Journal of Chemical Ecology | year = 2009| volume = 35| pages = 635–642| issue = 6 | doi=10.1007/s10886-009-9646-0|pmid=19475449 }} 22. ^{{cite journal | author = M. C. Ballesta-Acosta1, M. J. Pascual-Villalobos and B. Rodríguez | title = Short communication. The antifeedant activity of natural plant products towards the larvae of Spodoptera littoralis | journal = Spanish Journal of Agricultural Research | year = 2008| volume = 6 | issue = 1 | pages = 85–91 | doi=10.5424/sjar/2008061-304}} 23. ^{{cite journal | author = J. D. Martín| title = New diterpenoids extractives of Maytenus dispermus|journal = Tetrahedron | year = 1973| volume = 29| issue = 17| pages = 2553–2559| doi=10.1016/0040-4020(73)80172-3}} 24. ^{{cite journal |author1=H B Bode |author2=A Zeeck |lastauthoramp=yes | journal = J Chem Soc Perkin Trans 1 | year = 2000 | volume = 323 |issue=3 | doi = 10.1039/a908387a | title = Structure and biosynthesis of kendomycin, a carbocyclic ansa-compound from Streptomyces | pages = 323–328}} 25. ^[https://web.archive.org/web/20060829132137/http://www.chem.wisc.edu/~burke/Kendo.htm Burke Research Group] University of Wisconsin 26. ^{{cite journal |vauthors=Jansen R, Gerth K, Steinmetz H, Reinecke S, Kessler W, Kirschning A, Müller R | title = Elansolid A3, a Unique p-Quinone Methide Antibiotic from Chitinophaga sancti.| journal = Chem. Eur. J. | year = 2011 | pmid = 21626585 | doi=10.1002/chem.201100457 | volume=17 | issue=28 | pages=7739–44}} 27. ^{{cite journal |vauthors=Thiem DA, Sneden AT, Khan SI, Tekwani BL | title = Bisnortriterpenes from Salacia madagascariensis.| journal = J Nat Prod | year = 2005 | volume = 68 | issue = 2 | pages = 251–254 | doi=10.1021/np0497088}} 28. ^{{cite journal |vauthors=Setzer WN, Holland MT, Bozeman CA, Rozmus GF, Setzer MC, Moriarity DM, Reeb S, Vogler B, Bates RB, Haber WA | title = Isolation and frontier molecular orbital investigation of bioactive quinone-methide triterpenoids from the bark of Salacia petenensis.| journal = Planta Med | year = 2001 | volume = 67 | issue = 1 | pages = 65–69 | pmid = 11270725 | doi=10.1055/s-2001-10879}} 29. ^{{cite journal |vauthors=Chávez H, Estévez-Braun A, Ravelo AG, González AG | title = New phenolic and quinone-methide triterpenes from Maytenus amazonica.| journal = J Nat Prod | year = 1999 | volume = 62 | issue = 3 | pages = 434–436 | pmid = 10096852 | doi=10.1021/np980412+}} 30. ^{{cite journal |vauthors=González AG, Alvarenga NL, Bazzocchi IL, Ravelo AG, Moujir L | title = A new bioactive norquinone-methide triterpene from Maytenus scutioides.| journal = Planta Med | year = 1998 | volume = 64 | issue = 8 | pages = 767–771 | pmid = 10075545 | doi=10.1055/s-2006-957581}} External links
2 : Quinone methides|Functional groups |
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