Abstract
The syntheses, molecular and crystal structures, NMR spectroscopic study, and DFT computational study of naphthologs of mono-bridged (X = –, O, S, Se, and Te) tetraarylethene (BAE-1s) 11–25 with α,α-, β,β-, and α,β-dinaphthalenyl substituents have been reported. The BAE-1s have been prepared by Barton–Kellog twofold extrusion from the respective chalcogenothiones and diazomethylenebisnaphthylenes. Complete assignments of 1H- and 13C-NMR spectra of 11–25 have been made through 2-dimensional correlation spectroscopy (DQF-COSY, HSQC, HMBC, and NOESY). The corresponding intermediates, thiiranes 33–47, have been also isolated (except 38), and their molecular and crystal structures have been determined. The molecular structures of BAE-1s 12–15, 20, and 22–25 adopted folded-twisted conformations with considerably folded (φ = 30°–57°) tricyclic moieties. The α,α- and α,β-dinaphthalenyl derivatives are more overcrowded than β,β-dinaphthalenyl derivatives. The relief of the steric strain due to the overcrowding around C9 = C9′ caused by the presence of naphthalenyl substituents was achieved by their twisting around the single bonds that connect the α-naphthalenyl and β-naphthalenyl moieties to C9′. The 1H-NMR spectra have shown shielding of H2, H7 of 11–25 and the pronounced deshielding of H8′, H8″ of α,α-dinaphthalenyl-substituted BAE-1s 13–15 in contrast to β,β-dinaphthalenyl-substituted BAE-1s 16–20. The upfield shifts of H2, H7 suggested conformations in which these hydrogens are located above the planes of the opposing naphthalene rings. DFT calculations of 11–20 have been performed at B3LYP/6-31G(d) and B3LYP/SDD. The results have shown that the global minima of BAE-1s without a chalcogen bridge 11 and 16 are twisted (–sc,–sc)-C 2-t conformations. The global minima of BAE-1s with a chalcogen bridge are folded-twisted (–sc,–ac)-C 1-ft conformations for α,α-dinaphthalenyl-substituted BAE-1s 12–15 and either anti- or syn-(–sc,ac)-C 1-ft conformations for β,β-dinaphthalenyl-substituted BAE-1s 17–20. The pronounced differences between the α,α-dinaphthalenyl and the β,β-dinaphthalenyl derivatives are noted. Dispersion-corrected B3LYP calculations stabilize significantly the α,α-dinaphthalenyl derivatives versus the β,β-dinaphthalenyl derivatives. The geometrical parameters of BAEs-1 11–15 and 20, derived from their molecular X-ray structures and from their B3LYP-optimized geometries are in a good agreement.
Similar content being viewed by others
References
Shoham G, Cohen S, Suissa RM, Agranat I (1988) Stereochemistry of strained, overcrowded bistricyclic ethylenes. In: Stezowski JJ, Huang J-L, Shao M-C (eds) Molecular structure: chemical reactivity and biological activity. IUCr crystallographic symposia 2. Oxford University Press, Oxford, pp 290–312
Biedermann PU, Stezowski JJ, Agranat I (1998) In: Thummel RP (ed) Advances in theoretically interesting molecules, vol 4. JAI Press, Stamford, pp 245–322
Biedermann PU, Stezowski JJ, Agranat I (2001) Eur J Org Chem 2001:15–34
Biedermann PU, Agranat I (2014) Top Curr Chem. doi:10.1007/128_2014_534
de la Harpe C, van Dorp WA (1875) Ber Dtsch Chem Ges 8:1048–1050
Gurgenjanz G, von Konstanecki S (1895) Ber Dtsch Chem Ges 28:2310–2311
Meyer H (1909) Ber Dtsch Chem Ges 42:143–145
Meyer H (1909) Monatsh Chem 30:165–177
Schönberg A, Schütz O (1928) Ber Dtsch Chem Ges 61:478–479
Korenstein R, Muszkat KA, Fischer E (1976) J Photochem 5:345–353
Levy A, Biedermann PU, Cohen S, Agranat I (2000) J. Chem Soc Perkin Trans 2(2000):725–735
Levy A, Biedermann PU, Cohen S, Agranat I (2001) J Chem Soc Perkin Trans 2(2001):2329–2341
Feringa BL (2001) Acc Chem Res 34:504–513
Bell F, Waring DH (1949) J Chem Soc 1949:2689–2693
Harnik E, Herbstein FH, Schmidt GMJ (1951) Nature 168:158–160
Biedermann PU, Stezowski JJ, Agranat I (2001) Chem Commun 2001:954–955
Biedermann PU, Stezowski JJ, Agranat I (2006) Chem Eur J 12:3345–3354
Levy A, Pogodin S, Cohen S, Agranat I (2007) Eur J Org Chem 2007:5198–5211
Pogodin S, Suissa MR, Levy A, Cohen S, Agranat I (2008) Eur J Org Chem 2008:2887–2894
Assadi N, Pogodin S, Cohen S, Levy A, Agranat I (2009) Struct Chem 20:541–556
Bock H, Ruppert K, Herdtweck E, Herrmann WA (1992) Helv Chim Acta 75:1816–1824
Shi J, Chang N, Li C, Mei J, Deng C, Luo X, Liu Z, Bo Z, Dong YQ, Tang BZ (2012) Chem Commun 48:10675–10677
Hong Y, Lam JWY, Tang BZ (2009) Chem Commun 45:4332–4353
Zhou J, Chang Z, Jiang Y, He B, Du M, Lu P, Hong Y, Kwok HS, Qin A, Qui H, Zhao Z, Tang BZ (2013) Chem Commun 49:2491–2493
Pogodin S, Assadi N, Agranat I (2013) Struct Chem 24:1747–1757
Mei J, Hong Y, Lam JWY, Qin A, Tang Y, Tang BZ (2014) Adv Mater 26:5429–5479
Kanawati B, Genest A, Schmitt-Kopplin P, Lenoir D (2012) J Mol Model 18:5089–5095
Assadi N, Pogodin S, Cohen S, Agranat I (2013) Struct Chem 24:1229–1240
Bruker AXS GmbH (2002) SMART-NT V5.6, D-76181 Karlsruhe, Germany
Bruker AXS GmbH (2002) SAINT-NT V5.0, D-76181 Karlsruhe, Germany
Bruker AXS GmbH (2002) SHELXTL-NT V6.1, D-76181 Karlsruhe, Germany
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA, Vreven T Jr, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi S, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2004) Gaussian 03, Revision C.02. Gaussian Inc, Wallingford
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, Keith T, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, 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 O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2013) Gaussian 09, Revision D.01. Gaussian Inc., Wallingford
Becke AD (1993) J Chem Phys 98:5648–5652
Lee C, Yang W, Parr RG (1988) Phys Rev B 37:785–789
Grimme S (2011) WIREs Comput Mol Sci 1:211–228
Grimme S, Antony J, Ehrlich S, Krieg H (2010) J Chem Phys 132:154104–154119
Ehrlich S, Moellmann J, Grimme S (2013) Acc Chem Res 46:916–926
Barton DHR, Smith ER, Willis BJ (1970) J Chem Soc D: Chem Commun 1226–1226
Barton DHR (1996) Reason and Imagination: Reflections on Research, In: Organic Chemistry: Selected Papers of Derek H. R. Barton, Imperial College Press and World Scientific, Singapore, vol. 6, p. 489
Wang Z (2009) Barton-Kellogg olefination. In: Comprehensive organic name reactions and reagents, vol. 1, chapter 56. Wiley, New York, pp 249–253
Assadi N, Pogodin S, Cohen S, Agranat I (2012) Struct Chem 23:771–790
CCDC-1004535 (13), 1004536 (14), 1004537 (15), 1004538 (20), 1004539 (22), 1004540 (23), 1004541 (24), 1004542 (25), 1004543 (35), 1004544 (36), 1004545 (37), 1004546 (41), 1004547 (44) and 1004548 (47) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html. Accessed 20 Aug 2014 [or from the Cambridge Crystallographic Data Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033; email: deposit@ccdc.cam.ac.uk]
Lee J-S, Nyburg SC (1985) Acta Crystallogr C 41:560–567
Zefirov YV (1997) Crystallogr Rep 42:111–116 Transl. from Kristallografiya 42:122–128
Martin NH, Allen NW III, Moore KD, Vo L (1998) Theochem 454:161–166
Llabrès G, Baiwir M, Christiaens L, Piette JL (1979) Can J Chem 57:2967–2970
Bondi A (1964) J Phys Chem 68:441–451
Levy A, Biedermann PU, Cohen S, Agranat I (1998) Phosphorus Sulfur Silicon 136:139–142
Schneebeli ST, Bochevarov AD, Friesner RA (2011) J Chem Theory Comput 7:658–668
Sousa SF, Fernandes PA, Ramos MJ (2007) J Phys Chem A 111:10439–10452
Pogodin S, Rae ID, Agranat I (2006) Eur J Org Chem 2006:5059–5068
Assadi N, Pogodin S, Agranat I (2011) Eur J Org Chem 2011:6773–6780
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Assadi, N., Pogodin, S., Cohen, S. et al. Variations of bistricyclic aromatic enes: mono-bridged tetraarylethene naphthologs. Struct Chem 26, 319–352 (2015). https://doi.org/10.1007/s11224-014-0482-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11224-014-0482-7