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DOI: 10.1055/a-2764-1105
Planar Chiral Sulfur Compound Derived from [2.2]Paracyclophane: Synthesis and Applications
Authors

Abstract
Over the past decade, planar chiral sulfur-containing [2.2]paracyclophanes have attracted increasing attention. This review offers a comprehensive overview of the strategies developed to access these appealing derivatives, along with their diverse applications in fields ranging from catalysis to materials science. The discussion is organized according to the type and position of the sulfur functional group within the [2.2]paracyclophane framework.
Keywords
Cyclophanes - Sulfur - Chirality - Stereoselective synthesis - Thiols - Sulfoxides - Thiophenes - SulfidesPublication History
Received: 26 September 2025
Accepted after revision: 03 December 2025
Article published online:
30 December 2025
© 2025. Thieme. All rights reserved.
Georg Thieme Verlag KG
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References
- 1a Wu S, Felder S, Brom J. et al. Adv Opt Mater 2024; 12: 2400934
- 1b Hassan Z, Spuling E, Knoll DM, Bräse S. Angew Chem Int Ed 2020; 59: 2156
- 2 Vincent A, Deschamps D, Martzel T. et al. J Org Chem 2016; 81: 3961
- 3a Brown CJ, Farthing AC. Nature 1949; 164: 915
- 3b Cram DJ, Steinberg H. J Am Chem Soc 1951; 73: 5691
- 4 Gibson SE, Knight JD. Org Biomol Chem 2003; 1: 1256
- 5a Paradies J. Synthesis 2011; 3749
- 5b Hassan Z, Spuling E, Knoll DM, Lahann J, Bräse S. Chem Soc Rev 2018; 47: 6947
- 5c Felder S, Wu S, Brom J, Micouin L, Benedetti E. Chirality 2021; 33: 506
- 6a Morisaki Y, Chujo Y. Polym Chem 2011; 2: 1249
- 6b Hu S-M, Lee C-Y, Ramli TC. et al. Adv Funct Mater 2024; 34: 2313511
- 7a Elacqua E, MacGillivray LR. Eur J Org Chem 2010; 6883
- 7b Marrocchi A, Tomasi I, Vaccaro L. Isr J Chem 2012; 52: 41
- 7c Morisaki Y, Chujo Y. Bull Chem Soc Jpn 2019; 92: 265
- 7d Teng J-M, Zhang D-W, Chen C-F. ChemPhotoChem 2022; 6: e202100228
- 7e Liu W, Li H, Huo Y, Yao Q, Duan W. Molecules 2023; 28: 2891
- 7f Felder S, Delcourt M-L, Contant D. et al. Mater Chem C 2023; 11: 2053
- 7g Hassan Z. Adv Funct Mater 2024; 34: 2311828
- 7h Tappert H, Bräse S. Macromol Rapid Commun 2025; 46: 2500145
- 8a Aly AA, Brown AB. Tetrahedron 2009; 65: 8055
- 8b Rowlands GJ. Isr J Chem 2012; 52: 60
- 8c David ORP. Tetrahedron 2012; 68: 8977
- 8d Weiland KJ, Gallego A, Mayor M. Eur J Org Chem 2019; 3073
- 9 Kane VV, Gerdes A, Grahn W. et al. Tetrahedron Lett 2001; 42: 373
- 10 Ernst L, Wittkowski L. Eur J Org Chem 1999; 1653
- 11 Hitchcock PB, Rowlands GJ, Seacome RJ. Org Biomol Chem 2005; 3: 3873
- 12 Jones PG, Ernst L, Dix I, Wittkowski L. Acta Cryst Sect C 2000; 56: 239
- 13 Michalík M, Poliak P, Lukeš V. Acta Chim Slov 2016; 9: 6
- 14 Hou X-L, Wu X-W, Dai L-X, Cao B-X, Sun J. Chem Commun 2000; 1195
- 15 Marchand A, Maxwell A, Mootoo B, Pelter A, Reid A. Tetrahedron 2000; 56: 7331
- 16 Enders M, Friedmann CJ, Plessow PN. et al. Chem Commun 2015; 51: 4793
- 17 Ogawa S, Nakajo S, Muraoka H, Kawai Y, Sato R. J Sulfur Chem 2009; 30: 293
- 18 Pelter A, Mootoo B, Maxwell A, Reid A. Tetrahedron Lett 2001; 42: 8391
- 19 Menichetti S, Faggi C, Lamanna G, Marrocchi A, Minuti L, Taticchi A. Tetrahedron 2006; 62: 5626
- 20 Lohier J-F, Foucoin F, Jaffres P-A. et al. Org Lett 2008; 10: 1271
- 21 Beqa L, Deschamps D, Perrio S, Gaumont A-C, Knoppe S, Bürgi T. J Phys Chem C 2013; 117: 21619
- 22 Li M, Ma J, Wang L, Wu K, Zhou Y-G, Yu Z. J Org Chem 2025; 90: 9593
- 23a Kurose R, Nishii Y, Miura M. Org Lett 2021; 23: 2380
- 23b He F, Ma Y, Zhao L, Duan W, Chen J, Song C. Org Lett 2012; 14: 5436
- 24 Hicks C, Duffy B, Hargaden GC. Org Chem Front 2014; 1: 716
- 25 Zhang L, Ogawa K, Ghiviriga I, Dolbier Jr WR. J Org Chem 2009; 74: 6831
- 26 Wu K, Dolbier Jr WR, Battiste MA, Zhai Y. Mendeleev Commun 2006; 146
- 27 Kreis M, Bräse S. Adv Synth Catal 2005; 347: 313
- 28 Kreis M, Nieger M, Bräse S. J Organomet Chem 2006; 691: 2171
- 29 Mungalpara MN, Plieger PG, Rowlands GJ. Adv Synth Catal 2021; 363: 1069
- 30 Rowlands GJ, Seacome RJ. Beilstein J Org Chem. 2009 5(9)
- 31 Friedmann C, Bräse S. Synlett 2010; 774
- 32 Cram DJ, Day AC. J Org Chem 1966; 31: 1227
- 33 Taguchi J, Omoto Y, Uto K. et al. Adv Synth Catal 2025; 367: e202400986
- 34 Zhang X, Zhou Y, Yu Z-X, Tung C-H, Xu Z. Angew Chem Int Ed 2025; 64: e202420667
- 35 Reich HJ, Yelm KE. J Org Chem 1991; 56: 5672
- 36 Hitchcock PB, Rowlands GJ, Parmar R. Chem Commun 2005; 4219
- 37 Rowlands GJ. Org Biomol Chem 2008; 6: 1527
- 38 Morisaki Y, Hifumi R, Lin L, Inoshita K, Chujo Y. Polym Chem 2012; 3: 2727
- 39 Morisaki Y, Inoshita K, Shibata S, Chujo Y. Polym J 2015; 47: 278
- 40 Henderson WR, Fagnani DE, Grolms J, Abboud KA, Castellano RK. Helv Chim Acta 2019; 102: e1900047
- 41 Parmar R, Coles MP, Hitchcock PB, Rowlands GJ. Synthesis 2010; 24: 4177
- 42 Enders D, Ludwig M, Raabe G. Chirality 2012; 24: 215
- 43 Morisaki Y, Hifumi R, Lin L, Inoshita K, Chujo Y. Chem Lett 2012; 41: 990
- 44 Gelat F, Lohier J-F, Gaumont A-C, Perrio S. Adv Synth Catal 2011; 2015: 357
- 45 Pu Y, Smaldone AM, Adrio J, Walsh P. J Chem Sci 2025; 16: 18167
- 46 Martzel T, Lohier J-F, Gaumont A-C, Brière J-F, Perrio S. Adv Synth Catal 2017; 359: 96
- 47 van Lindert HCA, Koeberg-Telder A, Cerfontain H. Recl Trav Chim Pays-Bas 1992; 111: 379
- 48 De Ridder DJA, Goubitz K, Fontijn M, Capkova P, Dova E, Schenk H. Acta Crystallogr Sect B 2001; B57: 780
- 49 van Lindert HCA, van Doorn JA, Bakker BH, Cerfontain H. Recl Trav Chim Pays-Bas 1996; 115: 167
- 50 Christoph H, Grunenberg J, Hopf H. et al. Chem Eur J 2008; 14: 5604
- 51 Braddock DC, MacGilp ID, Perry BG. Adv Synth Catal 2004; 346: 1117
- 52 Yuan S, Liao C, Zheng W-H. Org Lett 2021; 23: 4142
- 53a Higuchi H, Kobayashi E, Sakata Y, Misumi S. Tetrahedron 1986; 42: 1731
- 53b Kannen N, Otsubo T, Misumi S. Bull Chem Soc Jpn 1976; 49: 3208
- 53c Kannan A, Hopf H, Dix I, Jones PG, Ernst L. Can J Chem 2017; 95: 278
- 54 Deschamps D, Gazzeh H, Bonciani A, Richards CJ, Gaumont A-C, Perrio S. Eur J Org Chem 2024; 27: e202301181
- 55 Kannen N, Otsubo T, Sakata Y, Misumi S. Bull Chem Soc Jpn 1976; 49: 3307
- 56 Truesdale EA, Cram DJ. J Org Chem 1980; 45: 3974
- 57 Kannan A, Dix I, Hopf H, Jones PG. Acta Crystallogr Sect E 2005; 61: 03562
- 58a Tatemitsu H, Otsubo T, Sakata Y, Misumi S. Tetrahedron Lett 1975; 16: 3059
- 58b Otsubo T, Kitasawa M, Misumi S. Chem Lett 1977; 6: 977
- 58c Otsubo T, Kohda T, Misumi S. Bull Chem Soc Jpn 1980; 53: 512
- 58d Machida H, Tatemitsu H, Otsubo T, Sakata Y, Misumi S. Bull Chem Soc Jpn 1980; 53: 2943
- 58e Higuchi H, Takatsu K, Otsubo T, Sakata Y, Misumi S. Tetrahedron Lett 1982; 23: 671
- 59 Otsubo T, Horita H, Misumi S. Synth Commun 1976; 6: 591
- 60 Schneebeli ST, Kamenetska M, Cheng Z. et al. J Am Chem Soc 2011; 133: 2136
- 61 Bléger D, Kreher D, Mathevet F. et al. Angew Chem Int Ed 2008; 47: 8412
- 62 Deschamps D, Lohier J-F, Richards CJ, Gaumont A-C, Perrio S. J Org Chem 2021; 86: 507
- 63 Frank D, Nieger M, Friedmann C, Lahann J, Bräse S. Isr J Chem 2012; 52: 143
- 64 Aly AA. Org Biomol Chem 2003; 1: 756
- 65 Dočekal V, Koucký F, Císařová I, Veselý J. Nat Commun 2024; 15: 3090
- 66a Meyer-Eppler G, Sure R, Schneider A, Schnakenburg G, Grimme S, Lützen A. J Org Chem 2014; 79: 6679
- 66b Bondarenko L, Dix I, Hinrichs H, Hopf H. Synthesis 2004; 2751
- 66c Yanagawa A, Tsuchiya M, Inoue R, Morisaki YJ. Mater Chem C 2023; 11: 986
- 66d Duan W, Ma Y, Qu B, Zhao L, Chen J, Song C. Tetrahedron Asymmetry 2012; 23: 1369
- 67a Hitchcock PB, Hodgson ACC, Rowlands GJ. Synlett 2006; 2625
- 67b Meyer-Eppler G, Vogelsang E, Benkhäuser C, Schneider A, Schnakenburg G, Lützen A. Eur J Org Chem 2013; 4523
- 67c Sawada R, Gon M, Nakamura J, Morisaki Y, Chujo Y. Chirality 2018; 30: 1109
- 68a Cakici M, Bräse S. Eur J Org Chem 2012; 6132
- 68b Kitagaki S, Ohta Y, Tomonaga S, Takahashi R, Mukai C. Tetrahedron Asymmetry 2011; 22: 986
- 68c Cakici M, Gu Z-G, Nieger M, Bürck J, Heinke L, Bräse S. Chem Commun 2015; 51: 4796
- 68d Kitagaki S, Sugisaka K, Mukai C. Org Biomol Chem 2015; 13: 4833
- 68e Braun C, Spuling E, Heine NB, Cakici M, Nieger M, Bräse S. Adv Synth Catal 2016; 358: 1664
- 68f Gon M, Morisaki Y, Chujo Y. Chem Eur J 2017; 23: 6323
- 68g Mandle RJ, Goodby JW. Liq Cryst 2018; 45: 1567
- 68h Namba G, Mimura Y, Imai Y, Inoue R, Morisaki Y. Chem Eur J 2020; 26: 14871
- 68i Yanagawa A, Inoue R, Morisaki Y. Chem Commun 2024; 60: 1468
- 69 Tsuchiya M, Maeda H, Inoue R, Morisaki Y. Chem Commun 2021; 57: 9256
- 70a Morisaki Y, Gon M, Sasamori T, Tokitoh N, Chujo Y. J Am Chem Soc 2014; 136: 3350
- 70b Miki N, Maeda H, Inoue R, Morisaki Y. ChemistrySelect 2021; 6: 12970
- 70c Asakawa R, Tabata D, Miki N, Tsuchiya M, Inoue R, Morisaki Y. Eur J Org Chem 2021; 5725
- 70d Tsuchiya M, Inoue R, Tanaka K, Morisaki Y. Chem Asian J 2022; 17: e202200418
- 71 Kitagaki S, Murata S, Asaoka K. et al. Chem Pharm Bull 2018; 66: 1006
- 72a Morisaki Y, Sawada R, Gon M, Chujo Y. Chem Asian J 2016; 11: 2524
- 72b Sasai Y, Tsuchida H, Kakuta T, Ogoshi T, Morisaki Y. Mater Chem Front 2018; 2: 791
- 72c Sasai Y, Inoue R, Morisaki Y. Bull Chem Soc Jpn 2020; 93: 1193
- 72d Tabata D, Inoue R, Sasai Y, Morisaki Y. Bull Chem Soc Jpn 2022; 95: 595
- 72e Jikuhara K, Inoue R, Morisaki Y. Sci Rep 2023; 13: 22647
- 73a Ortner B, Hübner H, Gmeiner P. Tetrahedron Asymmetry 2001; 12: 3205
- 73b Löber S, Ortner B, Bettinetti L, Hübner H, Gmeiner P. Tetrahedron Asymmetry 2002; 13: 2303
- 73c Kreis M, Friedmann CJ, Bräse S. Chem Eur J 2005; 11: 7387
- 73d Kitagaki S, Ueda T, Mukai C. Chem Commun 2013; 49: 4030
- 74a Zhang T-Z, Dai L-X, Hou X-L. Tetrahedron Asymmetry 2007; 18: 251
- 74b Kitagaki S, Ohta Y, Takahashi R, Komizu M, Mukai C. Tetrahedron Lett 2013; 54: 384
- 75 Fan Y, He J, Liu L. et al. Angew Chem Int Ed 2023; 62: e202304623
- 76 Zhao Y, Wang X-Q, Yu Y-J, Zhou Y-G. J Org Chem 2021; 86: 1262
- 77 Zhao Y, Ding Y-X, Wu B, Zhou Y-G. J Org Chem 2021; 86: 10788
- 78 Zhao Y, Li X, Deng W-H, Wu B, Liao R-Z, Zhou Y-G. J Org Chem 2024; 89: 321
- 79a Yu S, Bao H, Zhang D, Yang X. Nat Commun 2023; 14: 5239
- 79b Jayasundera K, Kusmus DNM, Deuilhé L. et al. Org Biomol Chem 2016; 14: 10848
- 80 Cram DJ, Harris Jr. FL. J Am Chem Soc 1967; 89: 4642
- 81 Lv Y, Mou C, Liu Q. et al. Org Lett 2024; 26: 1584
- 82 Jiang B, Han L, Li Y-L. et al. J Org Chem 2012; 77: 1701
- 83 El-Shaieb KM, Mourad A-FE, Hassan AA. Z Naturforsch B 2015; 70: 843
- 84 Schneider JF, Fröhlich R, Paradies J. Isr J Chem 2012; 52: 76
- 85a Schneider JF, Falk FC, Fröhlich R, Paradies J. Eur J Org Chem 2010; 12: 2265
- 85b Schneider JF, Fröhlich R, Paradies J. Synthesis 2010; 20: 3486
- 85c Lu Y, Ma Y, Yang S, Ma M, Chu H, Song C. Tetrahedron Asymmetry 2013; 24: 1082
- 86 Breugst M, Houk KN. J Org Chem 2014; 79: 6302
- 87 Kitagaki S, Shimo E, Takeda S. et al. Heterocycles 2021; 103: 678
- 88 Aly AA, Bräse S, Weis P. J Mol Struct 2019; 1178: 311
- 89 Duan W, Han Y, Liu Q. et al. Tetrahedron Lett 2017; 58: 271
- 90 Guyard L, Dumas C, Miomandre F, Pansu R, Renault-Méallet R, Audebert P. New J Chem 2003; 27: 1000
- 91 Dix I, Hopf H, Jones PG. Acta Crystalogr Sect C 1999; 55: 756
- 92 Chen C-H, Zheng W-H. Org Lett 2021; 23: 5554
- 93 Knoll DM, Šimek H, Hassan Z, Bräse S. Eur J Org Chem 2019; 6198
- 94 Zhou K, Wu R-R, Zhong X-R. et al. Chem Commun 2025; 61: 11665
- 95 Sarbu LG, Bahrin LG, Jones PG, Birsa LM, Hopf H. Beilstein J Org Chem 2015; 11: 1917
- 96 Bahrin LG, Hopf H, Jones PG, Birsa ML, Sarbu LG. Molecules 2020; 25: 5262
- 97 Mézière C, Allain M, Oliveras-Gonzalez C. et al. Chirality 2018; 30: 568
- 98 Guyard L, Nguyen Dinh An M, Audebert P. Adv Mater 2001; 13: 133
- 99 Salhi F, Collard DM. Adv Mater 2003; 15: 81
- 100 Dang D, Zhang H, Xu Y. et al. ACS Nano 2019; 13: 11863
- 101 Weiland KJ, Brandl T, Atz K. et al. J Am Chem Soc 2019; 141: 2104
- 102 Zafra JL, Molina Ontoria A, Mayorga Burrezo P. et al. J Am Chem Soc 2017; 139: 3095
- 103 Weiland KJ, Münch N, Gschwind W, Häussinger D, Mayor M. Helv Chim Acta 2019; 102: e1800205
- 104 Salhi F, Lee B, Metz C, Bottomley LA, Collard DM. Org Lett 2002; 4: 3195
- 105 Guyard L, Audebert P, Dolbier WR, Duan J-X. J Electroanal Chem 2002; 537: 189
- 106 Guyard L, Audebert P. Electrochem Commun 2001; 3: 164
- 107 Chang YJ, Watanabe M, Chou P-T, Chow TJ. Chem Commun 2012; 48: 726
- 108 Chang YJ, Chow TJ. Tetrahedron 2009; 65: 4726
- 109 Morisaki Y, Inoshita K, Shibata S, Chujo Y. Polym J 2015; 47: 278
- 110 Hasegawa M, Kobayakawa K, Matsuzawa H. et al. Chem Eur J 2017; 23: 3267
- 111 Kobayakawa K, Hasegawa M, Sasaki H. et al. Chem Asian J 2014; 9: 2751
- 112 Lu J, Gu W, Wei J. et al. Mater Chem C 2016; 4: 9576
- 113 Wang X, Zhang X, Sun L. et al. Sci Adv 2018; 4: eaat5780
- 114 Morisaki Y, Lin L, Chujo Y. Polym Bull 2009; 62: 737
- 115 Ren L, Han Y, Hou X, Ni Y, Wu J. Chem Eur J 2024; 30: e202304088
- 116 Upmann D, Koneczny M, Rass J, Jones PG. Z Naturforsch B 2019; 74: 389
- 117 Abdel-Latif FF, El-Shaieb KM, El-Deen AG. Z Naturforsch 2011; 66b: 965
See for example:
For representative examples of trilayered structures, see:
For tetralayered structures, see:
For DFT calculations: