Synthesis, Crystal Structures and Properties of Carbazole-based [6]helicenes Fused with an Azine Ring

Overview

Journal Beilstein J Org Chem

Specialty Chemistry

Date 2021 Jan 25

PMID 33488827

Authors

Daria I Tonkoglazova

Anna V Gulevskaya

Konstantin A Chistyakov

Olga I Askalepova

Affiliations

Soon will be listed here.

Abstract

Novel carbazole-based [6]helicenes fused with an azine ring (pyridine, pyrazine or quinoxaline) have been prepared through a five-step synthetic sequence in good overall yields. Commercially available 2,3-dihaloazines were used as starting materials. To discern the effect of merging an azine moiety within a helical skeleton, the X-ray structures, UV-vis absorption and fluorescence spectra of the helicenes were investigated and compared to that of the parent carbazole-based [6]helicene (7-phenanthro[3,4-]carbazole).

References

Verbiest , Elshocht , Kauranen , Hellemans , Snauwaert , Nuckolls . Strong enhancement of nonlinear optical properties through supramolecular chirality . Science. 1998; 282(5390):913-5. DOI: 10.1126/science.282.5390.913. View

Rickhaus M, Mayor M, Juricek M . Strain-induced helical chirality in polyaromatic systems. Chem Soc Rev. 2016; 45(6):1542-56. DOI: 10.1039/c5cs00620a. View

Vacek J, Chocholousova J, Stara I, Stary I, Dubi Y . Mechanical tuning of conductance and thermopower in helicene molecular junctions. Nanoscale. 2015; 7(19):8793-802. DOI: 10.1039/c5nr01297j. View

Shi L, Liu Z, Dong G, Duan L, Qiu Y, Jia J . Synthesis, structure, properties, and application of a carbazole-based diaza[7]helicene in a deep-blue-emitting OLED. Chemistry. 2012; 18(26):8092-9. DOI: 10.1002/chem.201200068. View

Hirano K, Inaba Y, Takasu K, Oishi S, Takemoto Y, Fujii N . Gold(I)-catalyzed polycyclizations of polyenyne-type anilines based on hydroamination and consecutive hydroarylation cascade. J Org Chem. 2011; 76(21):9068-80. DOI: 10.1021/jo2018119. View

Nakano K, Hidehira Y, Takahashi K, Hiyama T, Nozaki K . Stereospecific synthesis of hetero[7]helicenes by Pd-catalyzed double N-arylation and intramolecular O-arylation. Angew Chem Int Ed Engl. 2005; 44(43):7136-8. DOI: 10.1002/anie.200502855. View

Fujikawa T, Segawa Y, Itami K . Synthesis and Structural Features of Quadruple Helicenes: Highly Distorted π Systems Enabled by Accumulation of Helical Repulsions. J Am Chem Soc. 2016; 138(10):3587-95. DOI: 10.1021/jacs.6b01303. View

Gingras M, Felix G, Peresutti R . One hundred years of helicene chemistry. Part 2: stereoselective syntheses and chiral separations of carbohelicenes. Chem Soc Rev. 2012; 42(3):1007-50. DOI: 10.1039/c2cs35111k. View

Bedard A, Vlassova A, Hernandez-Perez A, Bessette A, Hanan G, Heuft M . Synthesis, crystal structure and photophysical properties of pyrene-helicene hybrids. Chemistry. 2013; 19(48):16295-302. DOI: 10.1002/chem.201301431. View

10.

Sundar M, Talele H, Mande H, Bedekar A, Tovar R, Muller G . Synthesis of enantiomerically pure helicene like bis-oxazines from atropisomeric 7,7'-dihydroxy BINOL: Preliminary measurements of the circularly polarized luminescence. Tetrahedron Lett. 2014; 55(10):1760-1764. PMC: 3972822. DOI: 10.1016/j.tetlet.2014.01.108. View

11.

Phillips K, Katz T, Jockusch S, Lovinger A, Turro N . Synthesis and properties of an aggregating heterocyclic helicene. J Am Chem Soc. 2001; 123(48):11899-907. DOI: 10.1021/ja011706b. View

12.

Fujikawa T, Mitoma N, Wakamiya A, Saeki A, Segawa Y, Itami K . Synthesis, properties, and crystal structures of π-extended double [6]helicenes: contorted multi-dimensional stacking lattice. Org Biomol Chem. 2017; 15(21):4697-4703. DOI: 10.1039/c7ob00987a. View

13.

Aillard P, Voituriez A, Marinetti A . Helicene-like chiral auxiliaries in asymmetric catalysis. Dalton Trans. 2014; 43(41):15263-78. DOI: 10.1039/c4dt01935k. View

14.

Upadhyay G, Talele H, Bedekar A . Synthesis and Photophysical Properties of Aza[n]helicenes. J Org Chem. 2016; 81(17):7751-9. DOI: 10.1021/acs.joc.6b01395. View

15.

Sawada Y, Furumi S, Takai A, Takeuchi M, Noguchi K, Tanaka K . Rhodium-catalyzed enantioselective synthesis, crystal structures, and photophysical properties of helically chiral 1,1'-bitriphenylenes. J Am Chem Soc. 2012; 134(9):4080-3. DOI: 10.1021/ja300278e. View

16.

Shiva Kumar K, Bhaskar B, Siddi Ramulu M, Praveen Kumar N, Ashfaq M, Pal M . Metal catalyst free cyclization of 3-alkynyl substituted 2-(indol-3-yl)quinoxalines in TFA alone: a new synthesis of indolophenazines. Org Biomol Chem. 2016; 15(1):82-87. DOI: 10.1039/c6ob02340a. View

17.

Passeri R, Aloisi G, Elisei F, Latterini L, Caronna T, Fontana F . Photophysical properties of N-alkylated azahelicene derivatives as DNA intercalators: counterion effects. Photochem Photobiol Sci. 2009; 8(11):1574-82. DOI: 10.1039/b9pp00015a. View

18.

Weimar M, da Costa R, Lee F, Fuchter M . A scalable and expedient route to 1-aza[6]helicene derivatives and its subsequent application to a chiral-relay asymmetric strategy. Org Lett. 2013; 15(7):1706-9. DOI: 10.1021/ol400493x. View

19.

Huang Q, Jiang L, Liang W, Gui J, Xu D, Wu W . Inherently Chiral Azonia[6]helicene-Modified β-Cyclodextrin: Synthesis, Characterization, and Chirality Sensing of Underivatized Amino Acids in Water. J Org Chem. 2016; 81(8):3430-4. DOI: 10.1021/acs.joc.6b00130. View

20.

Mohamed R, Mondal S, Guerrera J, Eaton T, Albrecht-Schmitt T, Shatruk M . Alkynes as Linchpins for the Additive Annulation of Biphenyls: Convergent Construction of Functionalized Fused Helicenes. Angew Chem Int Ed Engl. 2016; 55(39):12054-8. DOI: 10.1002/anie.201606330. View