1,2,3,4,5-Cyclopentanepentol, also namedcyclopentane-1,2,3,4,5-pentol or1,2,3,4,5-pentahydroxycyclopentane is achemical compound with formulaC 5H 10O 5 or(–CHOH–) 5, whosemolecule consists of a ring of fivecarbon atoms (acyclopentane skeleton), each connected to onehydrogen and onehydroxylgroup.[1] The unqualified term "cyclopentanepentol" usually refers to this compound. There are four distinctstereoisomers with this same structure.[2]
The compound is a five-foldalcohol of cyclopentane, and technically a cyclicsugar alcohol (acyclitol). However it is very rarely found in nature, and therefore it has received much less attention than the ubiquitous six-carbon version,inositol.[3]
There are four distinct stereoisomers of cyclopentane-1,2,3,4,5-pentol, distinguished by the position of the hydroxyls relative to the mean plane of the ring. All have a plane of symmetry, and therefore are not chiral. One naming convention for the isomers labels each carbon number 1-5 with "α" for the side of the ring plane with most hydroxyls (three or more), and "β" for the other side. Another convention lists the hydroxyls on the majority side and then those on the minority side, with the two groups separated by a slash (and a "0" is written when the second list would be empty).[4]
1α,2α,3α,4α,5α,1,2,3,4,5/0, orall-cis (all hydroxyls on the same side). CAS 34322-89-9. Long needles, melting point 283 °C (darkens ar 220 °C).[2][5] Obtained from cyclopentane-1α,2α-epoxi-3α,4α,5α-triol by treatment withhydrogen bromide to obtain cyclopentane-1β-bromo-2α,3α,4α,5α-tetrol, followed bybenzoylation and treatment withDMSO andsodium bicarbonate.[5]
1α,2α,3α,4α,5β or1,2,3,4/5. CAS 18939-02-1.[2] Soluble in hotethanol.[3] Melting point 220 °C[3] or 209-210 °C.[6] Obtained bysolvolysis of two tetra-O-acetyl-O-tosyl-cyclopentanepentol,[3] and also by hydroxylation of 3,4,5-trihydroxy-1-cyclopentenes.[6]
1α,2α,3α,4β,5β or1,2,3/4,5. CAS 18939-07-6.[2] Soluble in ethanol.[3] Melting point 168-169 °C,[3] or 176 °C.[6] Obtained by deamination of (1,4/2,3,5)-5-amino-1,3-di-O-acetyl-2,3-O-cyclohexylidene-1,2,3,4-cycopentanetetrol,[3] and also by hydroxylation of 3,4,5-trihydroxy-1-cyclopentenes.[6]
1α,2α,3β,4α,5β or1,2,4/3,5. CAS 57784-52-8.[2] Melting point 149.5-150.5 °C.[3] Obtained from cyclopent-4-ene-1,3/2-triol byepoxidation and subsequenthydrolysis;[7] also by acid hydrolysis of an anhydro-cyclopentanepentol, DL-1,2-anhydro-4,5-O-cyclohexylidene-1,2,3,4,5-cyclopentanepentol;[3] and also from a D-xylo-pentodialdose.[8]
The last three isomers interconvert by heating them at about 104 °C with 95%acetic acid in the presence of astrong acid. The conversion between 1,2,3,4/5 and 1,2,3/4,5 is faster and entails the hydrogen and hydroxyl switching places on either of the two carbon atoms located between an "α" and a "β" position. The formation of 1,2,4/3,5 is much slower and equilibrium is reached only after many days. The relative stabilities are 1,2,4/3,5 > 1,2,3/4,5 > 1,2,3,4/5, with equilibrium ratios 72 : 17.5 : 10.5.[3]
The isomers can be identified qualitatively by their mobility in paper ionophoresis in a solution ofcalcium acetate andacetic acid, and revealed with amanganese sulfate/potassium permanganate reagent. The mobilities of the isomers, relative to that ofcis-inositol, are 0.95 (12345/0), 0.44 (1234/5), 0.18 (123/45), and 0.04 (124/35). The variation is attributed to the formation ofchelates with thecalciumcations, with varying strengths depending on the number of hydroxyl pairs that can bind to the cation.[9] Similar results can be obtained withlanthanum cations andthin-layer chromatography.[10]
Mass spectrometry of the compound generates mainly the ion HO–CH=CH=CH=O+H (mass-charge ratio 73) and a neutral radicalC 2H 5O•.[11]
Trteatment of the derivative 3,4,5-tri-O-acetyl-1,2-O-ethylidene-(1,2,4/3,5)-cyclopentanepentol withtriphenylcarbeniumtetrafluoroborate[(C 6H 5) 3C]+ [BF 4]− to yield the cation 3,4,5-tri-O-acetyl-(1,2,4/3,5)-cyclopentanepentol-1,2-O-acetoxonium, which exhibits a peculiar 10-stage cyclic rearrangement.[12]
Cyclopentanepentols form dihydrogenphosphate esters analogous to inositol'sphytic acid esters.[13]
The related compound 1,2,3,4,5-pentakis(hydroxymethyl)-cyclopentane (a colourless viscous oil, soluble intert-butanol andDMSO) was synthesized in 1985 by L. M. Tolbert and others. It was hoped that dehydrativedimerization of this product would yielddodecahedrane.[14]
Organic compounds similar to (and possibly mimicking) glycoglycerolipids,[15] with a 1,2,4/3,5-cyclopentanepentol group connected to theglycerol core in place of thesugar group, have been found in several genera of marinesponges with widely separate ranges.[16][17][18][19][20][21]
Calditol is a substance found in thearchaeobacteria of the orderSulfolobales. It is anether that can be viewed as the condensation ofglycerol and 3α-hydroxymethyl-1α,2α,3β,4α,5β-hydroxy cyclopentane, forming an ether bridge –O– between the 1-carbon of the former and the 4-carbon of the latter.[22] Its seems to protects the cells in acidic environments.[23]
The 1,2,4/3,5 isomer was briefly described in 1963 by H. Z. Sable and others.[7] In 1968, Th. Posternak reported observation of 1,2,3,4/5 and 1,2,3/4,5, without the synthesis method.[28] Better synthesis methods for these three were published by S. J. Angyal and B. M. Luttrell in 1970.[3] Alternative methods for 1,2,3,4/5 and 1,2,3/4,5 were published in the same year by G. Wolczunowicz and others.[6] The remaining all-cis isomer (1,2,3,4,5/0) was synthesized in 1971 by F. G. Cocu and Posternak.[5]
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^CON and CBN IUPAC Commissions on Nomenclature (1968): "The Nomenclature of Cyclitols - Tentative Rules".European Journal of Biochemistry, volume 5, pages 1-12.doi:10.1111/j.1432-1033.1968.tb00328.x
^abcF. G. Cocu, Th. Posternak (1971): "Recherches dans la série des cyclitols XLII. Synthèses de cyclitols tout-cis dérivés du cyclopentane; préparation des cyclopentane-tétrol et - pentol tout-cis"Helvetica Chimica Acta, volume 54, issue 6, pages 1676-1687.doi:10.1002/hlca.19710540619
^abcdeG. Wolczunowicz, L. Bors, F. Cocu, Th. Posternak (1970): "Recherches dans la série des cyclitols, XLI. Synthèses de deux cyclopentane-pentols".Helvetica Chimica Acta, volume 53, issue 8, pages 2288-2295.doi:10.1002/hlca.19700530843
^abH. Z. Sable, Thelma Anderson, Bernadine Tolbert, Th. Posternak (1963): "Recherches dans la série des cyclitols XXXIII. Sur quelques cyclitols dérivés du cyclopentane".Helvetica Chimica Acta, volume 46, issue 4, pages 1157–1165.doi:10.1002/hlca.19630460410
^Barry V. L. Potter (1998) "Structure-Activity Relationships of Adenophostin A and Related Molecules at the 1-D-myo-Inositol 1,4,5-Trisphosphate Receptor".American Chemical Society Symposium Series, volume 718, chaper 10, pages 158-179doi:10.1021/bk-1999-0718.ch010
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^S. J. Angyal and J. A. Mills (1985): "Complexes of Carbohydrates with Metal Cations. XIV. Separation of Sugars and Alditols by Means of Their Lanthanum Complexes".Australian Journal of Chemistry, volume 38, issue 8, pages 1279–1285.doi:10.1071/CH9851279
^Gérard A. Singy and Armand Buchs (1975): "Etude par spectrométrie de masse de la fragmentation des cyclopentane-triols-1,2,3, des cyclopentane-tétrols et des cyclopentane-pentols".Helvetica Chimica Acta, volume 58, issue 7, pages 2164-2172.doi:10.1002/hlca.19750580729
^H. Paulsen, H. Behre (1969): "Cyclorearrangement of 3,4,5-Tri-O-acetyl-(1,2,4/3,5)-cyclopentanepentol-1,2-O-acetoxonium Tetrafluoroborate".Angewandte chemie - International Edition, volume 8, issue 11, pages 887–887.doi:10.1002/anie.196908871
^Marc Felemez, Gilbert Schlewer, David J. Jenkins, Vanessa Correa, Colin W. Taylor, Barry V. L. Potter, and Bernard Spiess (1999): "Inframolecular studies of the protonation of 1D-1,2,4/3,5-cyclopentanepentaol 1,3,4-trisphosphate, a ring-contracted analogue of 1D-myo-inositol 1,4,5-trisphosphate".Carbohydrate Research, volume 322, issues 1–2, pages 95-101.doi:10.1016/S0008-6215(99)00193-7
^Laren M. Tolbert, J. Carlin Gregory, Carolyn P. Brock (1985): "cis,cis,cis,cis-1,2,3,4,5-Pentakis(hydroxymethyl)-cyclopentane".Journal of Organic Chemistry, volume 50, issue 4, pages 548-548.doi:10.1021/jo00204a030
^G. Hölzl, P. Dörmann(2007): "Structure and function of glycoglycerolipids in plants and bacteria".Progress in Lipid Research, volume 46, issue 5, pages 225-243.PMID17599463doi:10.1016/j.plipres.2007.05.001
^V. Costantino, E. Fattorusso, and A. Mangoni (1993): "Isolation of five-membered cyclitol glycolipids, crasserides: unique glycerides from the spongePseudoceratina crassa"Journal of Organic Chemistry, volume 58, issue 1, pages 186–191.doi:10.1021/jo00053a034
^Jun'Ichi Kobayashi, Chun-Min Zeng and Masami Ishibashi (1993): "Keruffaride, a new all-ciscyclopentanepentol-containing metabolite from the okinawan marine spongeluffariella sp.".Journal of the Chemical Society, Chemical Communications, volume 1993, issue 1, pages 79–81.doi:10.1039/C39930000079
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^Dong-Kyoo Kim, Young Ja Lim. Jung Sun Kim, Jong Hee Park, Nam Deuk Kim, Kwang Sik Im, Jongki Hong, Jee H. Jung (1999) "A Cyclitol Derivative as a Replication Inhibitor from the Marine SpongePetrosia sp.Journal of Natural Products, volume 62, issue 5, pages 773-776.doi:10.1021/np9804785
^Yonghong Liu, Jee H. Jung, Tunhai Xu, Lijuan Long, Xiuping Lin, Hao Yin, Bin Yang, Xue-Feng Zhou, and Xianwen Yang (2011): "New cyclitol derivative from a spongeSarcotragus species".Natural Product Research, volume 25, issue 6, pages 648–652.doi:10.1080/14786419.2010.490213
^Antony V.Samrot and T.Thirunalasundari (2012): "[wprim.whocc.org.cn/admin/article/downloadAppendix?article=/upload/articleFile/P020160926333045048197.pdf&articleId=625657 Effect ofOscillatoria willei – a marine cyanobacterium on hydrazine induced toxicity]".Malaysian Journal of Microbiology, volume 8, issue 4, pages 229-234.ISSN1823-8262
^Harshal D. Kawale and Nanda Kishore (2019): "Production of hydrocarbons from a green algae (Oscillatoria) with exploration of its fuel characteristics over different reaction atmospheres".Energy, volume 178, pages 344-355.doi:10.1016/j.energy.2019.04.103
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