Configurational and Conformational Analysis of 5-deoxy-5-iodo-α,β-D-ribose with 3-Sphere Approach

Carmen-Irena Mitan; Emeric Bartha; Anca Hirtopeanu; Carmen Stavarache; Constantin Draghici; Miron Teodor Caproiu; Maria Maganu; Petru Filip

doi:doi:10.11648/j.ajqcms.20230701.11

Configurational and Conformational Analysis of 5-deoxy-5-iodo-α,β-D-ribose with 3-Sphere Approach

Carmen-Irena Mitan, Emeric Bartha, Anca Hirtopeanu, Carmen Stavarache, Constantin Draghici, Miron Teodor Caproiu, Maria Maganu, Petru Filip

Published in American Journal of Quantum Chemistry and Molecular Spectroscopy (Volume 7, Issue 1)

Received: 7 March 2023 Accepted: 27 March 2023 Published: 11 April 2023

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Abstract

Configurational and conformational analysis with 3-Sphere approach on selective iodination of α, β-methyl D-ribofuranose (2-α:2-β) with iodotriphenilphosphonium iodide complex [Ph₃P⁺I]I^- generated in situ, under RT, reflux, microwave and sonochemistry. Introduction of the unit and hypersphere trigonometric equations, under Hopf fibration and Lie algebra theories, on Lambert-Wu methods enable calculation of the dihedral angles from NMR data (¹³C chemical shift, vicinal coupling constant ³J_HH[Hz]) and the ratio of anomers. The conformation/configuration at anomeric position is cis: trans with axial:axial 3-α:3-β (³J_H1H2 3 or 4.5:0[Hz]) or equatorial:axial 3-α:3-β (³J_H1H2 6 or 4.5:0[Hz]) as state based on dihedral angles θ_H1H2[deg], recorded carbon chemical shift δ_Cn[deg] and VISION molecular models. The conformation of 3-β anomer is ³E, and in case of 3-α anomer ₃E on Altona’s map, the last having the succession of sign (+, -, -) with θ_H3H4^α trans-ee, or alternatively ³₂T conformation having the succession of sign (-, +, -) with θ_H3H4^α trans-aa. An equilibrium between ₃E^α and ³₂T^α was confirmed by ³J_H1H2 of 4.5[Hz], i.e. negative θ_H1H2^α with ³₂T and equatorial OCH₃, or positive θ_H1H2^α with ₃E and axial OCH₃. The APT experiment (attached proton test) demonstrated the formation of tetrahydro 2H-pyran-2-ol as side product after selective iodination of methyl 5-deoxy-β-D-ribofuranoside 2-β.

Published in	American Journal of Quantum Chemistry and Molecular Spectroscopy (Volume 7, Issue 1)
DOI	10.11648/j.ajqcms.20230701.11
Page(s)	1-8
Creative Commons	This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.
Copyright	Copyright © The Author(s), 2024. Published by Science Publishing Group

Keywords

3-Sphere, Dihedral Angles, Configuration, Conformation, Selective Iodination

References

[1]	J. B. Lambert, Structural chemistry in solution. R value, Acc. Chem. Res. 1971, 4, 87; doi.org/10.1021/ar50039aoo2.
[2]	H. R. Buys, Conformation of nonaromatic ring compounds LIVϯ: The calculation of dihedral angles from vicinal coupling constants is six membered ring compounds, Recl. Trav. Chim. Pays-Bas 1969, 1003; doi.org/10.1002/recl.19690880814.
[3]	J. B. Lambert, J. J. Papay, E. S. Magyar, M. K. Neuberg, Conformations of five membered rings. Limitations of the R-value methods, J. Am. Chem. Soc. 1973, 4458; doi.org/10.1021/ja007940073.
[4]	G. E. Wilson, T. J. Bazzone, Conformational studies of 1,3-thiazolidines, J. Am. Chem. Soc. 1974, 1465; doi.org/10.1021/ja00812a032.
[5]	A. Wu, D. Cremer, A. A. Auer, J. Gauss, Extension of the Karplus relationships for NMR Spin-Spin coupling constants to nonplanar ring systems: Pseudorotation of cyclopentane, J. Phys. Chem. A. 2002, 106, 657; doi.org/10.1021/jp013160l.
[6]	C.-I. Mitan, E. Bartha, A. Hartopeanu, C. Stavarache, C. Draghici, M. T. Caproiu, M. Manganu, I. Man, L. Tarko, F. Teodorescu, C. Deleanu, Anomeric ratio and dihedral angles of α,β-iodo-methyl-D-ribofuranose, ACS National Meeting, San Francisco, CA, 16-20 August 2020, ANYL 49 (poster) ID: 3396478; Demo - Morressier. Publisher: American Chemical Society, Washington, D. C; doi.10.1021/Scimeetings.Oc00571.
[7]	E. Fischer Ber. 1893, 26, 2400; doi.10.1002/cber.18930260327.
[8]	E. D. Dangerfield, S. A. Gulab, C. H. Plunkett, M. S. M. Timmer, B. L. Stocker, Carbohydrate Research 2010, 345, 1360; doi.org/10.1016/j.carres.2010.03.016.
[9]	P. J. Garegg, B. Samuelsson, Novel reagent for converting a hydroxy group into an iodo-group in carbohydrates with inversion of configuration, Perkin Trans 1, 1980, 2866; doi.org/10.1039/P19800002866.
[10]	P. R. Skaanderup, C. S. Poulsen, L. Hyldtoft, M. R. Jørgensen, R. Madsen, Regioselective conversion of primary alcohols into iodides in unprotected methyl furanosides and pyranosides, Synthesis 2002, 12, 1721; DOI: 10.1055/1-2002-33641.
[11]	C.-I. Mitan, E. Bartha, P. Filip, C. Draghici, M. T. Caproiu, R. Moriarty, Calculation of the dihedral angles of 1-α,-β-R-5-O-methanesulfonyl-2,3-O-isopropilidene-L-lyxose from NMR data with 3-sphere approach and Lambert-Wu R value. ACS National Meeting, Atlanta, GA, 22 - 26 August 2021, CARB (poster) ID: 3582748; Demo - Morressier. Publisher: American Chemical Society, Washington, D. C; doi.10.1021/Scimeetings.1c00922.
[12]	F.-H. Hu, L.-S. Wang, S.-F. Cai, Solubilities of triphenylphosphibe oxide in selected solvents, J. Chem. Eng. Data 2009, 54, 1382; doi.org/10.1021/je800842z.
[13]	J. Kennedy, J. Wu, K. Drew, I. Carmichael, A. S. Serianni, Carbohydrate reaction intermediates: Effect of ring oxygen protonation on the structure of conformation of aldofuranosyl rings, J. Am. Chem. Soc. 1997, 119, 8933; doi.org/10.1021/ja963727p.
[14]	J. L. Liras, V. M. Lynch, E. V. Anslyn, The ratio between endocyclic and exocyclic cleavage of pyranoside acetals is dependent upon the anomer, the temperature, the aglycon group, and the solvent, J. Am. Chem. Soc. 1997, 119, 8191; doi.org/10.1021/ja963807t.
[15]	O. St.-Jean, M. Prévost, Y. Guidon, Study of the endocyclic versus exocyclic C-O bond cleavage path ways of α- and β-methyl furanosides, J. Org. Chem. 2013, 2935; doi.org/10.1021/jo3027438.
[16]	R. Caputo, H. Kunz, D. Mastroianni, G. Palumbo, S. Pedatella, F. Solla, Eur. J. Chem. 1999, 3147; doi.org/10.1002/(SICI)1099-0690.
[17]	A. J. Hoog, Carbon-13 nuclear magnetic resonance spectra of some 2-substitute tetrahydropyrans, Organic Magnetic Resonance, 1974, 6, 233; doi.org/10.1002/mrc.1270060410.
[18]	R. J. Andersen, R. M. Dixon, B. T. Golding, Alkylcobalamins: formation by enantioselective alkylation of cob(I)alamin, 1H NMR spectra, and conformational analysis of the alkyl group, J. Organomet. Chem. 1992, 437, 227; doi.org/10.1016/0022-328x(92)83446-O.
[19]	M. J. Han, K. S. Yoo, Y. H. Kim, J. Y. Chang, The catalytic activity of ribose containing polymers for the hydrolysi of phosphordiester and cleavage of nucleic acid, Tetrahedron Lett, 2002, 43 (32), 5597; doi.org/10.1016/50040-4039(02)01123-1.
[20]	B. G. Roy, A. Roy, B. Achari, S. B. Mandal, A simple one-pot entry to cyclic ethers of varied ring sizes from diols via phosphonium ion induced iodination and base catalyzed Williamson etherification, Tetrahedron Lett. 2006, 47, 7783; doi.org/10.1016/j.tetlet.2006.08.090.
[21]	B. Classon, Z. Liu, New halogenation reagent systems useful for the mild one-step conversion of alcohols into iodides or bromides, J. Org. Chem. 1988, 53, 6126; doi.org/10.1021/jo00261a032.
[22]	N. K. Kochetkov, A. I. Usov, The reaction of carbohydrates with triphenyl phosphite methiodide and related compounds, Tetrahedron 1963, 19, 973-983; doi.org/10.1016/50040-4020/01799352.
[23]	C.-I. Mitan, E. Bartha, P. Filip, C. Draghici, M. T. Caproiu, R. M. Moriarty, Two isomers with trans-aa5,2 stereochemistry are calculated with 3-sphere trigonometric equations approach at circle inversion motion from NMR data. ACS National Meeting in Chicago, IL, August 21- 25, 2022, CARB 3717658, 22 august 2022, doi.org/10.1021/scimeetings.2c00523.
[24]	E. Bartha, C.-I. Mitan, C. Draghici, M. T. Caproiu, P. Filip, R. Moriarty, Program for prediction dihedral angle from vicinal coupling constant with 3-sphere approach, Rev. Roum. Chim. 2021, 66, 178-183; DOI: 10.33224/rrch.2021.66.2.08 (Eng).
[25]	C.-I. Mitan, E. Bartha, C. Draghici, M. T. Caproiu, P. Filip, R. M. Moriarty, Hopf fibration on relationship between dihedral angle θHnHn+1[deg] and vicinal angle ϕ[deg], angles calculated from NMR data with 3-sphere approach and Java Script, SciencePG 2022, 10, 21; DOI: 10.11648/j.sjc.20221001.13 (Eng).
[26]	P. C. Kline, A. S. Seriani, 13C-Enriched ribonucleosides: synthesis and applications of 13C-1H and 13C-13C spin coupling constants to assess furanose and N-glycoside bond conformations, J. Am. Chem. Soc. 1990, 112, 7373; doi.org./10 1021/ja001760043.

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Carmen-Irena Mitan, Emeric Bartha, Anca Hirtopeanu, Carmen Stavarache, Constantin Draghici, et al. (2023). Configurational and Conformational Analysis of 5-deoxy-5-iodo-α,β-D-ribose with 3-Sphere Approach. American Journal of Quantum Chemistry and Molecular Spectroscopy, 7(1), 1-8. https://doi.org/10.11648/j.ajqcms.20230701.11

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ACS Style

Carmen-Irena Mitan; Emeric Bartha; Anca Hirtopeanu; Carmen Stavarache; Constantin Draghici, et al. Configurational and Conformational Analysis of 5-deoxy-5-iodo-α,β-D-ribose with 3-Sphere Approach. Am. J. Quantum Chem. Mol. Spectrosc. 2023, 7(1), 1-8. doi: 10.11648/j.ajqcms.20230701.11

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AMA Style

Carmen-Irena Mitan, Emeric Bartha, Anca Hirtopeanu, Carmen Stavarache, Constantin Draghici, et al. Configurational and Conformational Analysis of 5-deoxy-5-iodo-α,β-D-ribose with 3-Sphere Approach. Am J Quantum Chem Mol Spectrosc. 2023;7(1):1-8. doi: 10.11648/j.ajqcms.20230701.11

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@article{10.11648/j.ajqcms.20230701.11,
  author = {Carmen-Irena Mitan and Emeric Bartha and Anca Hirtopeanu and Carmen Stavarache and Constantin Draghici and Miron Teodor Caproiu and Maria Maganu and Petru Filip},
  title = {Configurational and Conformational Analysis of 5-deoxy-5-iodo-α,β-D-ribose with 3-Sphere Approach},
  journal = {American Journal of Quantum Chemistry and Molecular Spectroscopy},
  volume = {7},
  number = {1},
  pages = {1-8},
  doi = {10.11648/j.ajqcms.20230701.11},
  url = {https://doi.org/10.11648/j.ajqcms.20230701.11},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajqcms.20230701.11},
  abstract = {Configurational and conformational analysis with 3-Sphere approach on selective iodination of α, β-methyl D-ribofuranose (2-α:2-β) with iodotriphenilphosphonium iodide complex [Ph3P+I]I- generated in situ, under RT, reflux, microwave and sonochemistry. Introduction of the unit and hypersphere trigonometric equations, under Hopf fibration and Lie algebra theories, on Lambert-Wu methods enable calculation of the dihedral angles from NMR data (13C chemical shift, vicinal coupling constant 3JHH[Hz]) and the ratio of anomers. The conformation/configuration at anomeric position is cis: trans with axial:axial 3-α:3-β (3JH1H2 3 or 4.5:0[Hz]) or equatorial:axial 3-α:3-β (3JH1H2 6 or 4.5:0[Hz]) as state based on dihedral angles θH1H2[deg], recorded carbon chemical shift δCn[deg] and VISION molecular models. The conformation of 3-β anomer is 3E, and in case of 3-α anomer 3E on Altona’s map, the last having the succession of sign (+, -, -) with θH3H4α trans-ee, or alternatively 32T conformation having the succession of sign (-, +, -) with θH3H4α trans-aa. An equilibrium between 3E α and 32T α was confirmed by 3JH1H2 of 4.5[Hz], i.e. negative θH1H2α with 32T and equatorial OCH3, or positive θH1H2α with 3E and axial OCH3. The APT experiment (attached proton test) demonstrated the formation of tetrahydro 2H-pyran-2-ol as side product after selective iodination of methyl 5-deoxy-β-D-ribofuranoside 2-β.},
 year = {2023}
}

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TY  - JOUR
T1  - Configurational and Conformational Analysis of 5-deoxy-5-iodo-α,β-D-ribose with 3-Sphere Approach
AU  - Carmen-Irena Mitan
AU  - Emeric Bartha
AU  - Anca Hirtopeanu
AU  - Carmen Stavarache
AU  - Constantin Draghici
AU  - Miron Teodor Caproiu
AU  - Maria Maganu
AU  - Petru Filip
Y1  - 2023/04/11
PY  - 2023
N1  - https://doi.org/10.11648/j.ajqcms.20230701.11
DO  - 10.11648/j.ajqcms.20230701.11
T2  - American Journal of Quantum Chemistry and Molecular Spectroscopy
JF  - American Journal of Quantum Chemistry and Molecular Spectroscopy
JO  - American Journal of Quantum Chemistry and Molecular Spectroscopy
SP  - 1
EP  - 8
PB  - Science Publishing Group
SN  - 2994-7308
UR  - https://doi.org/10.11648/j.ajqcms.20230701.11
AB  - Configurational and conformational analysis with 3-Sphere approach on selective iodination of α, β-methyl D-ribofuranose (2-α:2-β) with iodotriphenilphosphonium iodide complex [Ph3P+I]I- generated in situ, under RT, reflux, microwave and sonochemistry. Introduction of the unit and hypersphere trigonometric equations, under Hopf fibration and Lie algebra theories, on Lambert-Wu methods enable calculation of the dihedral angles from NMR data (13C chemical shift, vicinal coupling constant 3JHH[Hz]) and the ratio of anomers. The conformation/configuration at anomeric position is cis: trans with axial:axial 3-α:3-β (3JH1H2 3 or 4.5:0[Hz]) or equatorial:axial 3-α:3-β (3JH1H2 6 or 4.5:0[Hz]) as state based on dihedral angles θH1H2[deg], recorded carbon chemical shift δCn[deg] and VISION molecular models. The conformation of 3-β anomer is 3E, and in case of 3-α anomer 3E on Altona’s map, the last having the succession of sign (+, -, -) with θH3H4α trans-ee, or alternatively 32T conformation having the succession of sign (-, +, -) with θH3H4α trans-aa. An equilibrium between 3E α and 32T α was confirmed by 3JH1H2 of 4.5[Hz], i.e. negative θH1H2α with 32T and equatorial OCH3, or positive θH1H2α with 3E and axial OCH3. The APT experiment (attached proton test) demonstrated the formation of tetrahydro 2H-pyran-2-ol as side product after selective iodination of methyl 5-deoxy-β-D-ribofuranoside 2-β.
VL  - 7
IS  - 1
ER  -

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Author Information

Carmen-Irena Mitan

“C. D. Nenitescu” Institute of Organic and Supramolecular Chemistry, Splaiul Independentei 202B, Bucharest, Romania
Emeric Bartha

“C. D. Nenitescu” Institute of Organic and Supramolecular Chemistry, Splaiul Independentei 202B, Bucharest, Romania
Anca Hirtopeanu

“C. D. Nenitescu” Institute of Organic and Supramolecular Chemistry, Splaiul Independentei 202B, Bucharest, Romania
Carmen Stavarache

“C. D. Nenitescu” Institute of Organic and Supramolecular Chemistry, Splaiul Independentei 202B, Bucharest, Romania
Constantin Draghici

“C. D. Nenitescu” Institute of Organic and Supramolecular Chemistry, Splaiul Independentei 202B, Bucharest, Romania
Miron Teodor Caproiu

“C. D. Nenitescu” Institute of Organic and Supramolecular Chemistry, Splaiul Independentei 202B, Bucharest, Romania
Maria Maganu

“C. D. Nenitescu” Institute of Organic and Supramolecular Chemistry, Splaiul Independentei 202B, Bucharest, Romania
Petru Filip

“C. D. Nenitescu” Institute of Organic and Supramolecular Chemistry, Splaiul Independentei 202B, Bucharest, Romania

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Carmen-Irena Mitan, Emeric Bartha, Anca Hirtopeanu, Carmen Stavarache, Constantin Draghici, et al. (2023). Configurational and Conformational Analysis of 5-deoxy-5-iodo-α,β-D-ribose with 3-Sphere Approach. American Journal of Quantum Chemistry and Molecular Spectroscopy, 7(1), 1-8. https://doi.org/10.11648/j.ajqcms.20230701.11

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ACS Style

Carmen-Irena Mitan; Emeric Bartha; Anca Hirtopeanu; Carmen Stavarache; Constantin Draghici, et al. Configurational and Conformational Analysis of 5-deoxy-5-iodo-α,β-D-ribose with 3-Sphere Approach. Am. J. Quantum Chem. Mol. Spectrosc. 2023, 7(1), 1-8. doi: 10.11648/j.ajqcms.20230701.11

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AMA Style

Carmen-Irena Mitan, Emeric Bartha, Anca Hirtopeanu, Carmen Stavarache, Constantin Draghici, et al. Configurational and Conformational Analysis of 5-deoxy-5-iodo-α,β-D-ribose with 3-Sphere Approach. Am J Quantum Chem Mol Spectrosc. 2023;7(1):1-8. doi: 10.11648/j.ajqcms.20230701.11

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@article{10.11648/j.ajqcms.20230701.11,
  author = {Carmen-Irena Mitan and Emeric Bartha and Anca Hirtopeanu and Carmen Stavarache and Constantin Draghici and Miron Teodor Caproiu and Maria Maganu and Petru Filip},
  title = {Configurational and Conformational Analysis of 5-deoxy-5-iodo-α,β-D-ribose with 3-Sphere Approach},
  journal = {American Journal of Quantum Chemistry and Molecular Spectroscopy},
  volume = {7},
  number = {1},
  pages = {1-8},
  doi = {10.11648/j.ajqcms.20230701.11},
  url = {https://doi.org/10.11648/j.ajqcms.20230701.11},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajqcms.20230701.11},
  abstract = {Configurational and conformational analysis with 3-Sphere approach on selective iodination of α, β-methyl D-ribofuranose (2-α:2-β) with iodotriphenilphosphonium iodide complex [Ph3P+I]I- generated in situ, under RT, reflux, microwave and sonochemistry. Introduction of the unit and hypersphere trigonometric equations, under Hopf fibration and Lie algebra theories, on Lambert-Wu methods enable calculation of the dihedral angles from NMR data (13C chemical shift, vicinal coupling constant 3JHH[Hz]) and the ratio of anomers. The conformation/configuration at anomeric position is cis: trans with axial:axial 3-α:3-β (3JH1H2 3 or 4.5:0[Hz]) or equatorial:axial 3-α:3-β (3JH1H2 6 or 4.5:0[Hz]) as state based on dihedral angles θH1H2[deg], recorded carbon chemical shift δCn[deg] and VISION molecular models. The conformation of 3-β anomer is 3E, and in case of 3-α anomer 3E on Altona’s map, the last having the succession of sign (+, -, -) with θH3H4α trans-ee, or alternatively 32T conformation having the succession of sign (-, +, -) with θH3H4α trans-aa. An equilibrium between 3E α and 32T α was confirmed by 3JH1H2 of 4.5[Hz], i.e. negative θH1H2α with 32T and equatorial OCH3, or positive θH1H2α with 3E and axial OCH3. The APT experiment (attached proton test) demonstrated the formation of tetrahydro 2H-pyran-2-ol as side product after selective iodination of methyl 5-deoxy-β-D-ribofuranoside 2-β.},
 year = {2023}
}

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TY  - JOUR
T1  - Configurational and Conformational Analysis of 5-deoxy-5-iodo-α,β-D-ribose with 3-Sphere Approach
AU  - Carmen-Irena Mitan
AU  - Emeric Bartha
AU  - Anca Hirtopeanu
AU  - Carmen Stavarache
AU  - Constantin Draghici
AU  - Miron Teodor Caproiu
AU  - Maria Maganu
AU  - Petru Filip
Y1  - 2023/04/11
PY  - 2023
N1  - https://doi.org/10.11648/j.ajqcms.20230701.11
DO  - 10.11648/j.ajqcms.20230701.11
T2  - American Journal of Quantum Chemistry and Molecular Spectroscopy
JF  - American Journal of Quantum Chemistry and Molecular Spectroscopy
JO  - American Journal of Quantum Chemistry and Molecular Spectroscopy
SP  - 1
EP  - 8
PB  - Science Publishing Group
SN  - 2994-7308
UR  - https://doi.org/10.11648/j.ajqcms.20230701.11
AB  - Configurational and conformational analysis with 3-Sphere approach on selective iodination of α, β-methyl D-ribofuranose (2-α:2-β) with iodotriphenilphosphonium iodide complex [Ph3P+I]I- generated in situ, under RT, reflux, microwave and sonochemistry. Introduction of the unit and hypersphere trigonometric equations, under Hopf fibration and Lie algebra theories, on Lambert-Wu methods enable calculation of the dihedral angles from NMR data (13C chemical shift, vicinal coupling constant 3JHH[Hz]) and the ratio of anomers. The conformation/configuration at anomeric position is cis: trans with axial:axial 3-α:3-β (3JH1H2 3 or 4.5:0[Hz]) or equatorial:axial 3-α:3-β (3JH1H2 6 or 4.5:0[Hz]) as state based on dihedral angles θH1H2[deg], recorded carbon chemical shift δCn[deg] and VISION molecular models. The conformation of 3-β anomer is 3E, and in case of 3-α anomer 3E on Altona’s map, the last having the succession of sign (+, -, -) with θH3H4α trans-ee, or alternatively 32T conformation having the succession of sign (-, +, -) with θH3H4α trans-aa. An equilibrium between 3E α and 32T α was confirmed by 3JH1H2 of 4.5[Hz], i.e. negative θH1H2α with 32T and equatorial OCH3, or positive θH1H2α with 3E and axial OCH3. The APT experiment (attached proton test) demonstrated the formation of tetrahydro 2H-pyran-2-ol as side product after selective iodination of methyl 5-deoxy-β-D-ribofuranoside 2-β.
VL  - 7
IS  - 1
ER  -

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