Chemistry:1,2,3,4,5-cyclopentanepentol

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A cyclopentanepentol, more precisely a 1,2,3,4,5-cyclopentanepentol or cyclopentane-1,2,3,4,5-pentol is a chemical compound with formula C5H10O5 or (–CHOH–)5, whose molecule consists of a ring of five carbon atoms (a cyclopentane skeleton), each connected to one hydrogen and one hydroxyl group.[1] There are four distinct stereoisomers with this same structure.[2]

The compound is a five-fold alcohol of cyclopentane, and technically a cyclic sugar alcohol (a cyclitol). However it is very rarely found in nature, and therefore it has received much less attention than the ubiquitous six-carbon version, inositol.[3]

Isomers

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]

The four possible isomers are:[2]

  • 1α,2α,3α,4α,5α, 1,2,3,4,5/0, or all-cis (all hydroxyls on the same side). CAS 34322-89-9. Long needles, melting point 283 °C (darkens ar 220 °C).[2][5]
  • 1α,2α,3α,4α,5β or 1,2,3,4/5. CAS 18939-02-1.[2] Soluble in hot ethanol.[3] Melting point 220 °C[3] or 209-210 °C.[6] Obtained by solvolysis of two tetra-O-acetyl-O-tosylcyclopentanepentol,[3] and also by hydroxylation of 3,4,5-trihydroxy-1-cyclopentenes.[6]
  • 1α,2α,3α,4β,5β or 1,2,3/4,5. 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-l,2,3,4-cycopentanetetrol,[3] and also by hydroxylation of 3,4,5-trihydroxy-1-cyclopentenes.[6]
  • 1α,2α,3β,4α,5β or 1,2,4/3,5. CAS 57784-52-8.[2] Melting point 149.5-150.5 °C.[3] Obtained from cyclopent-4-ene-1,3/2-trio1 by epoxidation and subsequent hydrolysis,[7] and also by acid hydrolysis of an anhydro-cyclopentanepentol, DL-1,2-anhydro-4,5-O-cyclohexylidene-1,2,3/4,5-cyclopentanepentol.[3]

The last three isomers interconvert by heating them at about 104 °C with 95% acetic acid in the presence of a strong 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 of calcium acetate and acetic acid, and revealed with a manganese sulfate/potassium permanganate reagent. The mobilities of the isomers, relative to that of cis-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 of chelates with the calcium cations, with varying strengths depending on the number of hydroxyl pairs that can bind to the cation.[8] Similar results can be obtained with lanthanum cations and thin-layer chromatography.[9]

Derivatives and natural occurrences

Many esters are known, such as pentabenzoyls[2] and pentaacetyls.[3]

Trteatment of the derivative 3,4,5-tri-O-acetyl-1,2-O-ethylidene-(1,2,4/3,5)-cyclopentanepentol with triphenylcarbenium tetrafluoroborate [(C6H5)3C]+[BF4]− 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.[10]

Cyclopentanepentols form dihydrogenphosphate esters analogous to inositol's phytic acid esters.[11]

The related compound 1,2,3,4,5-pentakis(hydroxymethyl)-cyclopentane (a colourless viscous oil, soluble in tert-butanol and DMSO) was synthesized in 1985 by L. M. Tolbert and others. It was hoped that dehydrative dimerization of this product would yield dodecahedrane.[12]

Organic compounds similar (and possibly mimicking) glycoglycerolipids, with a 1,2,4/3,5-cyclopentanepentol group connected to the glycerol core in place of the sugar group, have been found in several genera of marine sponges with widely separate ranges.[13][14][15][16][17][18]

Calditol is a substance found in the archaeobacteria of the order Sulfolobales. It is an ether that can be viewed as the condensation of glycerol and cyclopentane-1α,2,2,3α,4α,5β-hexol (a cyclopentanepentol with an extra hydroxyl on carbon 2), forming an ether bridge –O– between the respective 1-carbons.[19]

History

The 1,2,4/3,5 isomer was brifly described in 1963 by H. Z. Sable and others.[7] In 1968, T. Posternak reported observation of 1,2,3,4/5 and 1,2,3/4,5, without the synthesis method.[20] 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 others.[5]

See also

References

  1. ↑ (2019) Entry 552295: 1,2,3,4-Cyclopentanepentol. Page at the PubChem website, accessed on 2019-07-23.
  2. ↑ 2.0 2.1 2.2 2.3 2.4 2.5 2.6 Peter M. Collins (2005): Dictionary of Carbohydrates, 2nd edition, page 268. CRC Press, 1304 pages. ISBN 9780849377655
  3. ↑ 3.00 3.01 3.02 3.03 3.04 3.05 3.06 3.07 3.08 3.09 3.10 3.11 S. J. Angyal and B. M. Luttrell (1970): "Cyclitols. XXXII. Cyclopentanepentols". Australian Journal of Chemistry, volume 23, issue 9, pages 1831-1838. {[doi|https://doi.org/10.1071/CH9701831}}
  4. ↑ 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
  5. ↑ 5.0 5.1 F. G. Cocu, T. Posternak (1971): Helvetica Chimica Acta, volume 54, pages 1676-.
  6. ↑ 6.0 6.1 6.2 6.3 6.4 G. 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
  7. ↑ 7.0 7.1 H. 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
  8. ↑ S. J. Angyal and J. A. Mills (1979): "Complexes of Carbohydrates with Metal Cations. XI. Paper Electrophoresis of Polyols in Solutions of Calcium Ions". Australian Journal of Chemistry, volume 32, issue 9, pages 1993–2001. doi:10.1071/CH9791993
  9. ↑ 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
  10. ↑ 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
  11. ↑ 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
  12. ↑ 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
  13. ↑ V. Costantino, E. Fattorusso, and A. Mangoni (1993): "Isolation of five-membered cyclitol glycolipids, crasserides: unique glycerides from the sponge Pseudoceratina crassa" Journal of Organic Chemistry, volume 58, issue 1, pages 186–191. doi:10.1021/jo00053a034
  14. ↑ Jun'Ichi Kobayashi, Chun-Min Zeng and Masami Ishibashi (1993): "Keruffaride, a new all-ciscyclopentanepentol-containing metabolite from the okinawan marine sponge luffariella sp.". Journal of the Chemical Society, Chemical Communications, volume 1993, issue 1, pages 79–81. doi:10.1039/C39930000079
  15. ↑ Masami Ishibashi, Chun-min Zeng, Jun'ichi Kobayashi (1993): "Keruffaride: Structure Revision and Isolation from Plural Genera of Okinawan Marine Sponges". Journal of Natural Products, volume 56, issue 10, pages 1856-1860. doi:10.1021/np50100a033
  16. ↑ E. Fattorusso, A. Mangoni (1997) "Marine Glycolipids". In Fortschritte der Chemie organischer Naturstoffe / Progress in the Chemistry of Organic Natural Products, volume 72, pp 215-301. doi:10.1007/978-3-7091-6527-0_3 ISBN 978-3-7091-7342-8
  17. ↑ 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 Sponge Petrosia sp. Journal of Natural Products, volume 62, issue 5, pages 773-776. doi:10.1021/np9804785
  18. ↑ 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 sponge Sarcotragus species". Natural Product Research, volume 25, issue 6, pages 648–652. doi:10.1080/14786419.2010.490213
  19. ↑ Yves Blériot, Edouard Untersteller, Benoît Fritz, and Pierre Sinaÿ (2001): "Total Synthesis of Calditol: Structural Clarification of this Typical Component of Archaea Order Sulfolobales". Chemistry: A European Journal, volume 8, issue 1, pages 240-246. doi:10.1002/1521-3765(20020104)8:1<240::AID-CHEM240>3.0.CO;2-G
  20. ↑ T. Posternak, and G. Wolczunovicz (1968): "Two new cyclopentanepentols". Naturwissenschaften, volume 55, issue 2, pages 82–83.doi:10.1007/BF00599491




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