Abstract
Oxidative photocyclization is the most widely used method to the synthesis of carbohelicenes, in particular the long carbohelicenes. It is also an efficient way to the synthesis of heterohelicenes including azahelicenes and thiahelicenes. In this chapter, we first introduce the synthesis of various carbohelicenes by different oxidative photocyclization strategy starting from the stilbene precursors. With two aryl groups in the stilbene precursors bearing heteroaromatic rings, azahelicenes and thiahelicenes can be regioselectively synthesized by the similar oxidative photocyclization. Based on this methodology, optically active helicenes can also be obtained after resolution, which makes these molecules applicable. Although this methodology has been widely utilized, it is difficult to be used for large-scale preparation because the photocyclization needs highly diluted solution (usually ca. 10−3 M) to prevent the [2+2] intermolecular cycloaddition. Recently, chemists found a solution—the continuous flow strategy—to solve the problem of large-scale preparation. Under the optimal condition, the helicene can be prepared at the rate of 60 mg/h.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Mallory FB, Mallory CW, Halpern EJ (1966) Paper presented at the first middle atlantic regional meeting of the American chemical society, Philadelphia
Flammang-Barbieux M, Nasielski J, Martin RH (1967) Synthesis of heptahelicene (1) benzo [c]phenanthro [4, 3-g]phenanthrene. Tetrahedron Lett 8(8):743–744
Scholz M, Mühlstädt M, Dietz F (1967) Chemie angeregter zustände. I. Mitt. Die richtung der photocyclisierung naphthalinsubstituierter äthylene. Tetrahedron Lett 8(7):665–668
Shen Y, Chen C-F (2012) Helicenes: synthesis and applications. Chem Rev 112(3):1463–1535
Gingras M (2013) One hundred years of helicene chemistry. part 1: non-stereoselective syntheses of carbohelicenes. Chem Soc Rev 42(3):968–1006
Hoffmann N (2014) Photochemical reactions applied to the synthesis of helicenes and helicene-like compounds. J Photochem Photobio C: Photochem Rev 19:1–19
Upadhyay GM, Talele HR, Sahoo S, Bedekar AV (2014) Synthesis of carbazole derived aza[7]helicenes. Tetrahedron Lett 55(39):5394–5399
Mallory FB, Regan CK, Bohen JM, Mallory CW, Bohen AA, Carroll PJ (2015) Discovery of deep-seated skeletal rearrangements in the photocyclizations of some tert-butyl-substituted 1,2-diarylethylenes. J Org Chem 80(1):8–17
Laarhoven WH, Boumans PGF (1975) Photodehydrocyclizations of stilbene-like compounds XIV photosynthesis and photoreactions of 1,2- and 1,14-diphenylpentahelicene derivatives. Recl Trav Chim Pays-Bas 94(5):114–118
Morgan DD, Horgan SW, Orchin M (1972) Photocyclization of stilbene analogs II. the photochemistry of 1-benzylidene-1,2,3,4-tetrahydrophenanthrene and 1-(1-naphthylmethylidene)-1,2,3,4-tetrahydrophenanthrene. Tetrahedron Lett 13(18):1789–1792
Laarhoven WH, Cuppen TJHM, Nivard RJF (1970) Photodehydrocyclizations in stilbene-like compounds—II. Tetrahedron 26(4):1069–1083
Dietz F, Scholz M (1968) Chemie angeregter zustände-IV: die photocyclisierung der drei isomeren distyrylbenzole. Tetrahedron 24(24):6845–6849
Mallory FB, Mallory CW (1983) An unusual fluorine atom rearrangement in the photocyclization of 1-fluoro[5]helicenes. J Org Chem 48(4):526–532
Ito N, Hirose T, Matsuda K (2014) Facile photochemical synthesis of 5,10-disubstituted [5]helicenes by removing molecular orbital degeneracy. Org Lett 16(9):2502–2505
Bedekar AV, Chaudhary AR, Shyam Sundar M, Rajappa M (2013) Expeditious synthesis of fluorinated styrylbenzenes and polyaromatic hydrocarbons. Tetrahedron Lett 54(5):392–396
Frimer AA, Kinder JD, Youngs WJ, Meador MAB (1995) Reinvestigation of the photocyclization of 1,4-Phenylene Bis(Phenylmaleic Anhydride)—preparation and structure of [5]Helicene 5,6-9,10-Dianhydride. J Org Chem 60(6):1658–1664
Thulin B, Wennerström O (1976) Propellicene or Bi-2,13-pentahelicenylene. Acta Chem Scand 30B:688–690
Moradpou A, Nicoud JF, Balavoin G, Kagan H, Tsoucari G (1971) Photochemistry with circularly polarized light—synthesis of optically active Hexahelicene. J Am Chem Soc 93 (9):2353–2354
Moradpour A, Kagan H, Baes M, Morren G, Martin RH (1975) Photochemistry with circularly polarized light—III: synthesis of helicenes using bis(arylvinyl) arenes as precursors. Tetrahedron 31(17):2139–2143
Biet T, Fihey A, Cauchy T, Vanthuyne N, Roussel C, Crassous J, Avarvari N (2013) Ethylenedithio-Tetrathiafulvalene-Helicenes: electroactive helical precursors with switchable chiroptical properties. Chem Eur J 19(39):13160–13167
Laarhove Wh, Brus GJM (1971) Polarographic data and deviations from coplanarity of helicene molecules. J Chem Soc B-Phys Org 7:1433–1434
Martin RH, Marchant M-J, Baes M (1971) Rapid syntheses of hexa and heptahelicene. Helv Chim Acta 54(1):358–360
Borkent JH, Laarhoven WH (1978) Thermal racemization of methyl-substituted hexahelicenes. Tetrahedron 34(16):2565–2567
Schwertel M, Hillmann S, Meier H (2013) Synthesis of highly substituted hexahelicenes. Helv Chim Acta 96(11):2020–2032
Martin RH, Flammang M, Cosyn JP, Gelbcke M (1968) 1. × .2. New syntheses of hexa- and heptahelicences. 3. Optical rotation and ord of heptahelicene. Tetrahedron Lett (31):3507–3510
Joly M, Defay N, Martin RH, Declerq JP, Germain G, Soubrierpayen B, Vanmeerssche M (1977) Bridged helicenes—3,15-ethano-[7]helicene and 3,15-(2-oxapropano)-[7]helicene—synthesis, h-1-nmr spectrography and x-ray-diffraction study. Helv Chim Acta 60(2):537–560
Martin RH, Eyndels C, Defay N (1974) Double helicenes: diphenanthro[4,3-a; 3′,4′-[o]picene and benzo[s]diphenanthro[4,3-a; 3′,4′-[o]picene. Tetrahedron 30(18):3339–3342
Liu LB, Katz TJ (1991) Bromine auxiliaries in photosyntheses of [5]helicenes. Tetrahedron Lett 32(47):6831–6834
Liu LB, Yang BW, Katz TJ, Poindexter MK (1991) Improved methodology for photocyclization reactions. J Org Chem 56(12):3769–3775
Tinnemans AHA, Laarhoven WH (1974) Photodehydrocyclizations in stilbene-like compounds. IX. 1,2-Phenyl shifts in the cyclization of 1-phenylpentahelicenes. J Am Chem Soc 96(14):4611–4616
Mallory FB, Mallory CW, Ricker WM (1975) Nuclear spin-spin coupling via nonbonded interactions. III. Effects of molecular structure on through-space fluorine-fluorine and hydrogen-fluorine coupling. J Am Chem Soc 97(16):4770–4771
Roose J, Achermann S, Dumele O, Diederich F (2013) Electronically connected [n]Helicenes: synthesis and chiroptical properties of enantiomerically pure (E)-1,2-Di([6]helicen-2-yl)ethenes. Eur J Org Chem 2013 (16):3223–3231
Mori K, Murase T, Fujita M (2015) One-step synthesis of [16]helicene. Angew Chem Int Ed 54(23):6847–6851
Tinnemans AHA, Laarhoven WH (1976) Photocyclisations of 1,4-diarylbut-1-en-3-ynes. Part III. Scope and limitations of the reaction. J Chem Soc, Perkin Trans 2 (10):1115–1120
Tinnemans AHA, Laarhoven WH (1973) A novel photocyclization, starting from 1,4-diarylbutenynes. Tetrahedron Lett 14(11):817–820
Veeramani K, Paramasivam K, Ramakrishnasubramanian S, Shanmugam P (1978) Photolysis of 4-Phenyl-3-vinylquinolines; a facile new route to the Benzo[k]phenanthridine System. Synthesis 1978 (11):855–857
Schultz AG, Hagmann WK (1978) Synthesis of indole-2-carboxylic esters. J Org Chem 43(17):3391–3393
Gingras M (2013) One hundred years of helicene chemistry. part 3: applications and properties of carbohelicenes. Chem Soc Rev 42(3):1051–1095
Aillard P, Voituriez A, Marinetti A (2014) Helicene-like chiral auxiliaries in asymmetric catalysis. Dalton Trans 43(41):15263–15278
Saleh N, Shen C, Crassous J (2014) Helicene-based transition metal complexes: synthesis. Properties and Applications. Chem Sci 5(10):3680–3694
Virieux D, Sevrain N, Ayad T, Pirat J-L (2015) Chapter two—helical phosphorus derivatives: synthesis and applications. In: Eric FVS, Christopher AR (eds) Advances in heterocyclic chemistry, vol Volume 116. Academic Press, pp 37–83. doi:http://dx.doi.org/10.1016/bs.aihch.2015.06.001
Reetz MT, Sostmann S (2001) 2,15-dihydroxy-hexahelicene (HELIXOL): synthesis and use as an enantioselective fluorescent sensor. Tetrahedron 57(13):2515–2520
Aloui F, El Abed R, Marinetti A, Ben Hassine B (2009) A new approach to 3,14-dihydroxyhexahelicene: resolution and attribution of the absolute configuration. C R Chim 12(1–2):284–290
Wachsmann C, Weber E, Czugler M, Seichter W (2003) New functional hexahelicenes–synthesis, chiroptical properties, X-ray crystal structures, and comparative data bank analysis of hexahelicenes. Eur J Org Chem 15:2863–2876
Terfort A, Gorls H, Brunner H (1997) The first helical-chiral phosphane ligands: rac-[5]- and rac-[6]-heliphos. Synthesis-Stuttgart 1:79–86
Moussa S, Aloui F, Hassine BB (2013) Synthesis and characterization of a new chiral pentacyclic phosphine. Synth Commun 43(2):268–276
Aloui F, Moussa S, Hassine BB (2011) Synthesis and characterisation of a new helically chiral ruthenium complex. Tetrahedron Lett 52(5):572–575
Aloui F, Hassine BB (2009) An alternative approach to 3-(diphenylphosphino)hexahelicene. Tetrahedron Lett 50(30):4321–4323
Reetz MT, Beuttenmuller EW, Goddard R (1997) First enantioselective catalysis using a helical diphosphane. Tetrahedron Lett 38(18):3211–3214
Yavari K, Moussa S, Ben Hassine B, Retailleau P, Voituriez A, Marinetti A (2012) 1H-phosphindoles as structural units in the synthesis of chiral helicenes. Angew Chem Int Ed 51 (27):6748–6752
Monteforte M, Cauteruccio S, Maiorana S, Benincori T, Forni A, Raimondi L, Graiff C, Tiripicchio A, Stephenson GR, Licandro E (2011) Tetrathiaheterohelicene phosphanes as helical-shaped chiral ligands for catalysis. Eur J Org Chem 2011 (28):5649–5658
Lefebvre Q, Jentsch M, Rueping M (2013) Continuous flow photocyclization of stilbenes–scalable synthesis of functionalized phenanthrenes and helicenes. Beilstein J Org Chem 9:1883–1890
Hernandez-Perez AC, Vlassova A, Collins SK (2012) Toward a visible light mediated photocyclization: Cu-based sensitizers for the synthesis of [5]helicene. Org Lett 14(12):2988–2991
Bédard A-C, Vlassova A, Hernandez-Perez AC, Bessette A, Hanan GS, Heuft MA, Collins SK (2013) Synthesis, crystal structure and photophysical properties of pyrene-helicene hybrids. Chem Eur J 19(48):16295–16302
Kagan H, Moradpou.A, Nicoud JF, Balavoin.G, Martin RH, Cosyn JP (1971) Photochemistry with circularly polarised light .2. Asymmetric synthesis of octa and nonahelicene. Tetrahedron Lett (27):2479–2482
Martin RH, Cosyn JP (1971) New synthesis of octahelicene involving non-interconvertible Dl—intermediates. Synth Commun 1(4):257–265
Cochez Y, Martin RH, Jespers J (1976) Helicenes: chemically induced asymmetric photosyntheses of helicenes skeletons. Isr J Chem 15(1–2):29–32
Laarhove Wh, Cuppen HJM (1973) Photodehydrocyclizations of stilbene-like compounds. 7. Synthesis and properties of double helicene, diphenanthro[3,4-C;3’,4’-L]chrysene. Recueil Des Travaux Chimiques Des Pays-Bas 92 (4):553–562
Laarhove Wh, Cuppen JHM (1971) Photodehydrocyclizations of stilbene-like compounds. 4. Synthesis of a double helicene rac and meso diphenanthro 3,4-C-3’4-1 chrysene. Tetrahedron Lett 2:163–164
Martin RH, Defay N, Eyndels C (1972) Studies in helicene series—determination of structure and of Dl configuration of a double helicene by indor and noe experiments. 18. Tetrahedron Lett 27:2731–2732
Martin RH, Baes M (1975) Helicenes–photosyntheses of [11]helicene, [12]helicene and [14]helicene. Tetrahedron 31(17):2135–2137
Martin RH, Morren G, Schurter JJ (1969) [13]helicene and [13]helicene-10,21-D2. Tetrahedron Lett 42:3683–3684
Hu J-Y, Feng X, Paudel A, Tomiyasu H, Rayhan U, Thuéry P, Elsegood MRJ, Redshaw C, Yamato T (2013) Synthesis, structural, and photophysical properties of the first member of the class of pyrene-based [4]helicenes. Eur J Org Chem 2013 (26):5829–5837
Hu J-Y, Paudel A, Seto N, Feng X, Era M, Matsumoto T, Tanaka J, Elsegood MRJ, Redshaw C, Yamato T (2013) Pyrene-cored blue-light emitting [4]helicenes: synthesis, crystal structures, and photophysical properties. Org Biomol Chem 11(13):2186–2197
Bock H, Subervie D, Mathey P, Pradhan A, Sarkar P, Dechambenoit P, Hillard EA, Durola F (2014) Helicenes from diarylmaleimides. Org Lett 16(6):1546–1549
De Silva O, Snieckus V (1971) Photochemical synthesis of Benzo[c]carbazole and Pyridocarbazoles. Synthesis 1971 (05):254–255
Waghray D, Zhang J, Jacobs J, Nulens W, Basarić N, Meervelt LV, Dehaen W (2012) Synthesis and structural elucidation of diversely functionalized 5,10-Diaza[5]Helicenes. J Org Chem 77(22):10176–10183
Waghray D, Cloet A, Van Hecke K, Mertens SFL, De Feyter S, Van Meervelt L, Van der Auweraer M, Dehaen W (2013) Diazadithia[7]Helicenes: synthetic exploration, solid-state structure, and properties. Chem Eur J 19 (36):12077-12085
Ben Braiek M, Aloui F, Moussa S, Tounsi M, Marrot J, Ben Hassine B (2013) Synthesis, X-ray analysis and photophysical properties of a new N-containing pentacyclic helicene. Tetrahedron Lett 54(40):5421–5425
Bucinskas A, Waghray D, Bagdziunas G, Thomas J, Grazulevicius JV, Dehaen W (2015) Synthesis, functionalization, and optical properties of Chiral Carbazole-based Diaza [6] Helicenes. J Org Chem 80(5):2521–2528
Upadhyay GM, Bedekar AV (2015) Synthesis and photophysical properties of bi-aza[5]Helicene and bi-aza[6]Helicene. Tetrahedron 71(34):5644–5649
Abbate S, Bazzini C, Caronna T, Fontana F, Gambarotti C, Gangemi F, Longhi G, Mele A, Sora IN, Panzeri W (2006) Monoaza[5]Helicenes. Part 2: synthesis, characterisation and theoretical calculations. Tetrahedron 62(1):139–148
Bazzini C, Brovelli S, Caronna T, Gambarotti C, Giannone M, Macchi P, Meinardi F, Mele A, Panzeri W, Recupero F, Sironi A, Tubino R (2005) Synthesis and characterization of some Aza[5]Helicenes. Eur J Org Chem 7:1247–1257
Martin RH, Deblecker M (1969) Synthesis of 4-Azahexahelicene (benzo[c]Phénanthro[1,2-f] Quinoline). Tetrahedron Lett 10(41):3597–3598
Aloui F, El Abed R, Ben Hassine B (2008) Synthesis of a new N-containing Hexahelicene. Tetrahedron Lett 49(9):1455–1457
Sato K, Yamagishi T, Arai S (2000) Synthesis of novel Azonia[5]Helicenes containing terminal thiophene rings. J Heterocycl Chem 37(4):1009–1014
Arai S, Ishikura M, Yamagishi T (1998) Synthesis of polycyclic azonia-aromatic compounds by photo-induced intramolecular quaternization: azonia derivatives of benzo[c]Phenanthrene, [5]Helicene and [6]Helicene. J Chem Soc Perkin Trans 1(9):1561–1567
Luo JK, Federspiel RF, Castle RN (1997) The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 19. Thieno[3’,2’:4,5]thieno[2,3-c]-naphtho[1,2-f]quinoline, thieno[3’,2’:4,5]thieno[2,3-c]naphtho[1,2-f][1,2,4]triazolo[4,3-a]quinoline and thieno[3’,2’:4,5]-thieno[2,3-c]naphtho[1,2-f]tetrazolo[1,5-a]quinoline. J Heterocycl Chem 34(5):1597–1601
Groen MB, Schadenb H, Wynberg H (1971) Synthesis and resolution of some heterohelicenes. J Org Chem 36 (19):2797-2809
Tedjamulia ML, Tominaga Y, Castle RN, Lee ML (1983) The synthesis of benzo[b]phenanthro[d]thiophenes and anthra[b]benzo[d]thiophenes. J Heterocycl Chem 20(4):861–866
Dopper JH, Oudman D, Wynberg H (1973) Use of thieno[2,3-b]thiophene in synthesis of heterohelicenes by double photocyclizations. J Am Chem Soc 95(11):3692–3698
Lehman P, Wynberg H (1974) The synthesis of a series of regularly annelated 2-methylheterohelicenes. Aust J Chem 27(2):315–322
Li C, Zhang Y, Zhang S, Shi J, Kan Y, Wang H (2014) From N, N-diphenyl-N-naphtho[2,1-b]thieno[2,3-b:3′,2′-d]dithiophene-5-yl-amine to propeller-shaped N, N, N-tri(naphtho[2,1-b]thieno[2,3-b:3′,2′-d]dithiophene-5-yl)-amine: syntheses and structures. Tetrahedron 70(25):3909–3914
Liu X, Yu P, Xu L, Yang J, Shi J, Wang Z, Cheng Y, Wang H (2013) Synthesis for the mesomer and racemate of thiophene-based double helicene under irradiation. J Org Chem 78(12):6316–6321
Waghray D, Dehaen W (2013) A fragment based approach toward thia[n]helicenes. Org Lett 15(12):2910–2913
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
Copyright information
© 2017 Springer-Verlag Berlin Heidelberg
About this chapter
Cite this chapter
Chen, CF., Shen, Y. (2017). Oxidative Photocyclization. In: Helicene Chemistry. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-53168-6_3
Download citation
DOI: https://doi.org/10.1007/978-3-662-53168-6_3
Published:
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-662-53166-2
Online ISBN: 978-3-662-53168-6
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)