"Through-space" indirect spin-spin couplings between hydrogen atoms formally separated by up to 18 covalent bonds have been detected by NMR experiments in model helical molecules. It is demonstrated that this coupling can provide crucial structural information on the molecular conformation in solution. The coupling pathways have been visualised and analysed by computational methods. The conformational dependence of the coupling is explained in terms of orbital interactions.

Institute of Inorganic Chemistry Slovak Academy of Sciences Dúbravská cesta 9 SK 84536 Bratislava Slovakia Email

Institute of Organic Chemistry and Biochemistry Czech Academy of Sciences Flemingovo nám 2 166 10 Prague 6 Czech Republic Email

Zobrazit více v PubMed

Dunitz J. D., X-Ray Analysis and the Structure of Organic Molecules, Wiley-VCH, Weinheim, 2nd edn, 1996.

Desiraju G. R., Vittal J. J. and Ramanan A., Crystal Engineering. A Textbook, World Scientific Publishing Co. Pte. Ltd., London, 2011.

Dračínský M., Buděšínský M., Warzajtis B., Rychlewska U. J. Phys. Chem. A. 2012;116:680–688. PubMed

Stará I. G. and Starý I., in Science of Synthesis, ed. J. S. Siegel and Y. Tobe, Thieme, Stuttgart, 2010, pp. 885–953.

Shen Y., Chen C. F. Chem. Rev. 2012;112:1463–1535. PubMed

Gingras M. Chem. Soc. Rev. 2013;42:968–1006. PubMed

Gingras M., Felix G., Peresutti R. Chem. Soc. Rev. 2013;42:1007–1050. PubMed

Gingras M. Chem. Soc. Rev. 2013;42:1051–1095. PubMed

Tanaka K., in Transition-Metal-Mediated Aromatic Ring Construction, ed. K. Tanak, Wiley, Hoboken, 2013, pp. 281–298.

Urbano A., Carreño M. C. Org. Biomol. Chem. 2013;11:699–708. PubMed

Bosson J., Gouin J., Lacour J. Chem. Soc. Rev. 2014;43:2824–2840. PubMed

Saleh N., Shen C. S., Crassous J. Chem. Sci. 2014;5:3680–3694.

Narcis M. J., Takenaka N. Eur. J. Org. Chem. 2014;2014:21–34.

Aillard P., Voituriez A., Marinetti A. Dalton Trans. 2014;43:15263–15278. PubMed

Chen C.-F. and Shen Y., Helicene Chemistry: From Synthesis to Applications, Springer-Verlag, Berlin, 2017.

Allen F. H. Acta Crystallogr., Sect. B: Struct. Sci. 2002;58:380–388. PubMed

Dračínský M., Storch J., Církva V., Císařová I., Sýkora J. Phys. Chem. Chem. Phys. 2017;19:2900–2907. PubMed

Buchta M., Rybáček J., Jančařík A., Kudale A. A., Buděšínský M., Chocholoušová J. V., Vacek J., Bednárova L., Císařová I., Bodwell G. J., Starý I., Stará I. G. Chem. - Eur. J. 2015;21:8910–8917. PubMed

Guo Y. D., Yan X. H., Xiao Y., Liu C. S. Sci. Rep. 2015;5:16731. PubMed PMC

Chen L., Wang Y. H., He B. R., Nie H., Hu R. R., Huang F., Qin A. J., Zhou X. S., Zhao Z. J., Tang B. Z. Angew. Chem., Int. Ed. 2015;54:4231–4235. PubMed

Quan X. F., Marvin C. W., Seebald L., Hutchison G. R. J. Phys. Chem. C. 2013;117:16783–16790.

Vacek J., Chocholoušová J. V., Stará I. G., Starý I., Dubi Y. Nanoscale. 2015;7:8793–8802. PubMed

Wijmenga S. S., van Buuren B. N. M. Prog. Nucl. Magn. Reson. Spectrosc. 1998;32:287–387.

Arnold W. D., Mao J. H., Sun H. H., Oldfield E. J. Am. Chem. Soc. 2000;122:12164–12168.

Bryce D. L., Wasylishen R. E. J. Mol. Struct. 2002;602:463–472.

Bagno A., Saielli G., Scorrano G. Chem. - Eur. J. 2002;8:2047–2056. PubMed

Pecul M., Sadlej J., Helgaker T. Chem. Phys. Lett. 2003;372:476–484.

Cybulski H., Pecul M., Sadlej J., Helgaker T. J. Chem. Phys. 2003;119:5094–5104.

Alkorta I., Elguero J. Int. J. Mol. Sci. 2003;4:64–92.

Contreras R. H., Barone V., Facelli J. C., Peralta J. E. Annu. Rep. NMR Spectrosc. 2003;51:167–260.

Tuttle T., Grafenstein J., Cremer D. Chem. Phys. Lett. 2004;394:5–13. PubMed

Bagno A., Rastrelli F., Saielli G. Prog. Nucl. Magn. Reson. Spectrosc. 2005;47:41–93.

Camacho P. S., Arachchige K. S. A., Slawin A. M. Z., Green T. F. G., Yates J. R., Dawson D. M., Woollins J. D., Ashbrook S. E. J. Am. Chem. Soc. 2015;137:6172–6175. PubMed

Hierso J. C. Chem. Rev. 2014;114:4838–4867. PubMed

Grzesiek S., Cordier F., Jaravine V., Barfield M. Prog. Nucl. Magn. Reson. Spectrosc. 2004;45:275–300.

Alkorta I., Elguero J., Denisov G. S. Magn. Reson. Chem. 2008;46:599–624. PubMed

Afonin A. V., Vashchenko A. V. Magn. Reson. Chem. 2010;48:309–317. PubMed

Dračínský M. Annu. Rep. NMR Spectrosc. 2017;90:1–40.

Mallory F. B., Mallory C. W., Ricker W. M. J. Org. Chem. 1985;50:457–461.

Mallory F. B., Mallory C. W., Butler K. E., Lewis M. B., Xia A. Q., Luzik E. D., Fredenburgh L. E., Ramanjulu M. M., Van Q. N., Francl M. M., Freed D. A., Wray C. C., Hann C., Nerz-Stormes M., Carroll P. J., Chirlian L. E. J. Am. Chem. Soc. 2000;122:4108–4116.

Kareev I. E., Quinones G. S., Kuvychko I. V., Khavrel P. A., Ioffe I. N., Goldt I. V., Lebedkin S. F., Seppelt K., Strauss S. H., Boltalina O. V. J. Am. Chem. Soc. 2005;127:11497–11504. PubMed

Emsley J. W., De Luca G., Lesage A., Longeri M., Mallory F. B., Mallory C. W. Phys. Chem. Chem. Phys. 2008;10:6534–6543. PubMed

Mallory F. B., Mallory C. W. J. Am. Chem. Soc. 1985;107:4816–4819.

Mallory F. B., Luzik E. D., Mallory C. W., Carroll P. J. J. Org. Chem. 1992;57:366–370.

Schaefer T., Chum K., Marat K., Wasylishen R. E. Can. J. Chem. 1976;54:800–804.

Hatnean J. A., Raturi R., Lefebvre J., Leznoff D. B., Lawes G., Johnson S. A. J. Am. Chem. Soc. 2006;128:14992–14999. PubMed

Hierso J. C., Evrard D., Luca D., Richard P., Cattey H., Hanquet B., Meunier P. J. Organomet. Chem. 2008;693:574–578.

Hierso J. C., Fihri A., Ivanov V. V., Hanquet B., Pirio N., Donnadieu B., Rebiere B., Amardeil R., Meunier P. J. Am. Chem. Soc. 2004;126:11077–11087. PubMed

Hierso J. C., Armspach D., Matt D. C. R. Chim. 2009;12:1002–1013.

Stepien M., Latos-Grazynski L., Szterenberg L., Panek J., Latajka Z. J. Am. Chem. Soc. 2004;126:4566–4580. PubMed

Dračínský M., Jansa P., Bouř P. Chem. - Eur. J. 2012;18:981–986. PubMed

Xiao Y. L., Mague J. T., Pascal R. A. J. Angew. Chem., Int. Ed. 2018;57:2244–2247. PubMed

žádný J., Jančařík A., Andronova A., Šámal M., Chocholoušová J. V., Vacek J., Pohl R., Šaman D., Císařová I., Stará I. G., Starý I. Angew. Chem., Int. Ed. 2012;51:5857–5861. PubMed

Helgaker T., Jaszunski M., Ruud K. Chem. Rev. 1999;99:293–352. PubMed

Pascal R. A., Zong J., Dougherty K. J., Geng X., Mague J. T. Tetrahedron. 2014;70:7518–7526.

Ruud K., Åstrand P. O., Taylor P. R. J. Am. Chem. Soc. 2001;123:4826–4833. PubMed

Dračínský M., Kaminský J., Bouř P. J. Chem. Phys. 2009;130:094106. PubMed

Dračínský M., Hodgkinson P. Chem.–Eur. J. 2014;20:2201–2207. PubMed

Ramsey N. F. Phys. Rev. 1953;91:303–307. PubMed

Grimme S. J. Comput. Chem. 2006;27:1787–1799. PubMed

Grimme S., Antony J., Ehrlich S., Krieg H. J. Chem. Phys. 2010;132:154104. PubMed

Dračínský M., Bouř P., Hodgkinson P. J. Chem. Theory Comput. 2016;12:968–973. PubMed

Jalaie M., Weatherhead S., Lipkowitz K. B., Robertson D. Electron. J. Theor. Chem. 1997;2:268–272.

Rempala P., King B. T. J. Chem. Theory Comput. 2006;2:1112–1118. PubMed

Rulíšek L., Exner O., Cwiklik L., Jungwirth P., Starý I., Pospíšil L., Havlas Z. J. Phys. Chem. C. 2007;111:14948–14955.

Šesták P., Wu J. Y., He J. Y., Pokluda J., Zhang Z. L. Phys. Chem. Chem. Phys. 2015;17:18684–18690. PubMed

Grimme S., Muck-Lichtenfeld C., Erker G., Kehr G., Wang H. D., Beckers H., Willner H. Angew. Chem., Int. Ed. 2009;48:2592–2595. PubMed

Malkina O. L., Malkin V. G. Angew. Chem., Int. Ed. 2003;42:4335–4338. PubMed

Malkina O. L., Křístková A., Malkin E., Komorovský S., Malkin V. G. Phys. Chem. Chem. Phys. 2011;13:16015–16021. PubMed

Marek R., Křístková A., Maliňáková K., Toušek J., Marek J., Hocek M., Malkina O. L., Malkin V. G. J. Phys. Chem. A. 2010;114:6689–6700. PubMed

Křístková A., Asher J. R., Malkin V. G., Malkina O. L. J. Phys. Chem. A. 2013;117:9235–9244. PubMed

Duval E., Koide S. Phys. Lett. 1964;8:314–315.