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Essential versus accidental isochrony of diastereotopic nuclei in NMR spectroscopy

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Abstract

Compounds where a non-stereogenic sp 2 atom (for instance the C atom of a benzene ring) is linked to a stereogenic sp 3 atom (for instance CHFCl) have several conformations where two diastereotopic nuclei become isochronous. This also happens in some cases when the sp 3 atom is non-stereogenic, the difference being related to the weighted value of the difference of absolute shieldings. The results here described seem to be in contradiction with experimental results pointing out that all diastereotopic nuclei are anisochronous. Two examples of typical diastereotopic nuclei involving C(sp 3)–C(sp 3) bonds, a propane and an ethane, were also discussed.

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References

  1. Field LD, Sternhell S, Kalman JR (2013) Organic structures from spectra, 5th edn. Wiley, Chichester

    Google Scholar 

  2. Laszlo P, Schleyer PVR (1964) J Am Chem Soc 86:1171–1179

    Article  CAS  Google Scholar 

  3. Senkler GH Jr, Gust D, Riccobono PX, Mislow K (1972) J Am Chem Soc 94:8626–8627

    Article  CAS  Google Scholar 

  4. Schiemenz GP, Rast H (1972) Tetrahedron Lett 12:1697–1700

    Article  Google Scholar 

  5. Nógrádi M (1981) Stereochemistry: basic concepts and applications. Pergamon Press, Oxford, p 123

    Google Scholar 

  6. Eliel EL (1982) Prostereoisomerism (prochirality). Top Curr Chem 105:1–76

    Article  CAS  Google Scholar 

  7. Weber U, Thiele H (1988) NMR spectroscopy: modern spectral analysis. Wiley, Weinheim, p 133

    Google Scholar 

  8. Sanders JKM, Hunter BK (1993) Modern NMR spectroscopy: a guide for chemists, 2nd edn. Oxford University Press, Oxford, pp 303–307

    Google Scholar 

  9. Mislow K (1999) Molecular chirality. In: Denmark SE (ed) Topics in stereochemistry, vol 22. Wiley, New York, pp 1–82

    Chapter  Google Scholar 

  10. Parzuchowski P, Böhmer V, Biali SE, Thondorf I (2000) Tetrahedron Asymmetry 11:2393–2402

    Article  CAS  Google Scholar 

  11. Tringali C (2001) Bioactive compounds from natural sources: isolation, characterisation and biological properties. Taylor and Francis, London, p 73

    Google Scholar 

  12. Allenhand A, Dobrenwend M (1985) J Am Chem Soc 107:6684–6688

    Article  Google Scholar 

  13. Faroozandeh M, Adams RW, Meharry NJ, Jeannerat D, Nilsson M, Morris GA (2014) Angew Chem Int Ed 53:6990–6992

    Article  Google Scholar 

  14. Sanders JKM, Williams DH (1971) J Am Chem Soc 93:641–645

    Article  Google Scholar 

  15. Schiemenz GP, Rast H (1971) Tetrahedron Lett 11:4685–4688

    Article  Google Scholar 

  16. Ditchfield R (1974) Mol Phys 27:789–807

    Article  CAS  Google Scholar 

  17. London F (1937) J Phys Radium 8:397–409

    Article  CAS  Google Scholar 

  18. Becke AD (1988) Phys Rev A 38:3098–3100

    Article  CAS  Google Scholar 

  19. Becke AD (1993) J Chem Phys 98:5648–5652

    Article  CAS  Google Scholar 

  20. Lee C, Yang W, Parr RG (1988) Phys Rev B 37:785–789

    Article  CAS  Google Scholar 

  21. Hariharan PA, Pople JA (1973) Theor Chim Acta 28:213–222

    Article  CAS  Google Scholar 

  22. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA Jr, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam NJ, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, revision D.01. Gaussian, Wallingford

    Google Scholar 

  23. Ditchfield R, Hehre WJ, Pople JA (1971) J Chem Phys 54:724–728

    Article  CAS  Google Scholar 

  24. Frisch MJ, Pople JA, Binkley JS (1984) J Chem Phys 80:3265–3269

    Article  CAS  Google Scholar 

  25. Reisse J, Ottinger R, Bickart P, Mislow K (1978) J Am Chem Soc 100:911–915

    Article  CAS  Google Scholar 

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Acknowledgments

Thanks are also given to the Ministerio de Economía y Competitividad of Spain (Project CTQ2012-13129-C02-02) and the Comunidad Autónoma de Madrid (Project Fotocarbon, S2013/MIT-2841). We warmly thank Professors Hans-Heinrich Limbach, Alain Fruchier, and Christian Roussel for invaluable comments on previous versions of this paper as well as one of the reviewers who suggested that we compare diastereotopicity and differences in energy.

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  1. Instituto de Química Médica (CSIC), Juan de la Cierva, 3, 28006, Madrid, Spain

    Ibon Alkorta & José Elguero

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  1. Ibon Alkorta
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  2. José Elguero
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Correspondence to Ibon Alkorta.

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Alkorta, I., Elguero, J. Essential versus accidental isochrony of diastereotopic nuclei in NMR spectroscopy. Struct Chem 27, 671–679 (2016). https://doi.org/10.1007/s11224-015-0607-7

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