TY - JOUR
T1 - 1,8,10-Trisubstituted anthracenyl hydrocarbons
T2 - Towards versatile scaffolds for multiple-H-bonded recognition arrays
AU - Forensi, Silvia
AU - Stopin, Antoine
AU - de Leo, Federica
AU - Wouters, Johan
AU - Bonifazi, Davide
N1 - Funding Information:
D.B. gratefully acknowledge the EU through the SGt-ERC (project: COLORLANDS), MSCA-RISE (project: INFUSION), MSCA-ITN (project: PHOTOTRAIN), IA-H2020 (project: DecoChrom) funding schemes for the financial support. A.S. thanks the DecoChrom project for his post-doctoral fellowship.
Publisher Copyright:
© 2020
PY - 2020/12/18
Y1 - 2020/12/18
N2 - In this work, we describe the synthesis of 1,8,10-trisubstituted anthracenyl scaffolds that, bearing boronic acid functionalities, can act as multiple H-bonding donor systems. The trisubstituted anthracenyl derivatives are synthesized following two main synthetic pathways. Whereas in the first approach trisubstituted anthracenyl derivatives are prepared through the regioselective addition of the relevant organomagnesium nucleophile to 1,8-dichloroanthraquinone, in the second avenue a triflate-bearing anthracene is prepared by reduction of the anthraquinone into the anthrone precursor and functionalized through metal-catalysed cross-coupling reactions. Complementary studies of the Na2S2O4-mediated reduction of 1,8-dichloroanthraquinone allowed to shed further light on the possible mechanism of formation of the anthrone precursor, suggesting the presence of a cis-diol intermediate undergoing antiperiplanar elimination. Solid-state X-ray diffraction investigations of the bisboronic acids show that the molecules self-assemble into dimers through the formation of four H-bonds established between the anti-syn conformers of the boronic acid moieties. 1H-NMR titrations between bisboronic acids and tetra H-bond acceptor, diisoquinolino-naphthyridine, showed a significant shift of the -B(OH)2 proton resonances, suggesting the presence of H-bonding interactions between both molecules.
AB - In this work, we describe the synthesis of 1,8,10-trisubstituted anthracenyl scaffolds that, bearing boronic acid functionalities, can act as multiple H-bonding donor systems. The trisubstituted anthracenyl derivatives are synthesized following two main synthetic pathways. Whereas in the first approach trisubstituted anthracenyl derivatives are prepared through the regioselective addition of the relevant organomagnesium nucleophile to 1,8-dichloroanthraquinone, in the second avenue a triflate-bearing anthracene is prepared by reduction of the anthraquinone into the anthrone precursor and functionalized through metal-catalysed cross-coupling reactions. Complementary studies of the Na2S2O4-mediated reduction of 1,8-dichloroanthraquinone allowed to shed further light on the possible mechanism of formation of the anthrone precursor, suggesting the presence of a cis-diol intermediate undergoing antiperiplanar elimination. Solid-state X-ray diffraction investigations of the bisboronic acids show that the molecules self-assemble into dimers through the formation of four H-bonds established between the anti-syn conformers of the boronic acid moieties. 1H-NMR titrations between bisboronic acids and tetra H-bond acceptor, diisoquinolino-naphthyridine, showed a significant shift of the -B(OH)2 proton resonances, suggesting the presence of H-bonding interactions between both molecules.
KW - Anthracene
KW - Boronic acids
KW - Hydrogen-bonds
KW - Polycyclic aromatic hydrocarbons
UR - http://www.scopus.com/inward/record.url?scp=85086790496&partnerID=8YFLogxK
U2 - 10.1016/j.tet.2020.131299
DO - 10.1016/j.tet.2020.131299
M3 - Article
AN - SCOPUS:85086790496
SN - 0040-4020
VL - 76
JO - Tetrahedron
JF - Tetrahedron
IS - 51
M1 - 131299
ER -