The Synthesis of Rigid Chromophore–Spacer–Chromophore Dyads and Three-Armed Triads by the 1,3-Dipolar Reaction of Cyclobutene Epoxides with Aromatic Dipolarophiles

Davor Margetić; Douglas N. Butler; Ronald N. Warrener

doi:10.1055/s-0033-1340305

Synthesis, Table of Contents

Synthesis 2013; 45(24): 3413-3425
DOI: 10.1055/s-0033-1340305

paper

The Synthesis of Rigid Chromophore–Spacer–Chromophore Dyads and Three-Armed Triads by the 1,3-Dipolar Reaction of Cyclobutene Epoxides with Aromatic Dipolarophiles

Davor Margetić*

^aLaboratory for Physical Organic Chemistry, Division of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, Bijenička c. 54, 10000 Zagreb, Croatia Fax: +385(1)4561008 Email: margetid@irb.hr

,

Douglas N. Butler

^bIntelligent Polymer Research Institute, Molecular Architecture Unit, University of Wollongong, Wollongong, NSW 2500, Australia

,

Ronald N. Warrener

^bIntelligent Polymer Research Institute, Molecular Architecture Unit, University of Wollongong, Wollongong, NSW 2500, Australia

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Abstract

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Abstract

A series of polyaromatic hydrocarbons (PAHs) or their aza derivatives were reacted as dipolarophiles with ring-fused cyclobutene epoxides (CEs) in the 1,3-dipolar cycloaddition protocol to form 1:1 cycloadducts. The dihydroforms of the PAH chromophores contained in the rigid alicyclic scaffold were dehydrogenated to regenerate the original PAH chromophore and constituted a new route to rigid chromophore-nσ-PAH dyads separated by an alicyclic scaffold. The anthracene 1:1 adduct derived from the reaction with the 5,8-dimethoxynaphthalene-containing CE was reacted a second time to produce stereoisomeric three-armed triads in which naphthalene chromophores were attached rigidly onto scaffold. Two approaches were used to generate the incipient cyclic 1,3-dipolar intermediates involved in cycloaddition process. The first method employed ring-opening of functionalised CEs, the other method produced the dipolar reagent in situ by loss of dinitrogen from the initially formed adduct resulting from treatment of fused norbornenes with 2,5-bis(trifluoromethyl)-1,3,4-oxadiazole.

Key words

cycloaddition - arenes - ylides - polycycles - dehydrogenation

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References

References
1 Warrener RN, Butler DN, Russell RA. Synlett 1998; 566

2a Warrener RN, Pitt IG, Butler DN. J. Chem. Soc., Chem. Commun. 1983; 1340
2b Margetić D, Briš A, Butler DN, Warrener RN. Tetrahedron 2013; 69: 7403

3a Golka A, Keyte PJ, Paddon-Row MN. Tetrahedron 1992; 48: 7663
3b Clayton AH, Ghiggino KP, Wilson GJ, Keyte PJ, Paddon-Row MN. Chem. Phys. Lett. 1992; 195: 249

4 Nadeau JM, Liu M, Waldeck DH, Zimmt MB. J. Am. Chem. Soc. 2003; 125: 15964

5a Warrener RN, Sun G, Johnston MR. Aust. J. Chem. 2003; 56: 269
5b Warrener RN, Margetić D, Sun G, Russell RA. Aust. J. Chem. 2003; 56: 263

6a Warrener RN. Eur. J. Org. Chem. 2000; 3363
6b Warrener RN, Butler DN, Margetic D, Pfeffer FM, Russell RA. Tetrahedron Lett. 2000; 41: 4671
6c Margetić D, Butler DN, Warrener RN. ARKIVOC 2002; (vi): 234
6d Foley PJ, Warrener RN. Synth. Commun. 2001; 31: 3011

7a Benkhoff J, Boese R, Klärner FG. Liebigs Ann./Recl. 1997; 501
7b Stoddart JF. Chem. Br. 1988; 24: 1203

8a Warrener RN, Shang M, Butler DN. Chem. Commun. 2001; 1550
8b Butler DN, Shang M, Warrener RN. Chem. Commun. 2001; 159

9 Warrener RN, Butler DN, Liu L, Margetić D, Russell RA. Chem. Eur. J. 2001; 7: 3406

10a Paddon-Row MN. Adv. Phys. Org. Chem. 2003; 38: 1
10b Gladkikh VS, Burshtein AI, Tavernier HL, Fayer MD. J. Phys. Chem. A 2002; 106: 6982
10c Goes M, de Groot M, Koeberg M, Verhoeven JW, Lokan NR, Shephard MJ, Paddon-Row MN. J. Phys. Chem. A 2002; 106: 2129
10d Napper AM, Read I, Kaplan R, Zimmt MB, Waldeck DH. J. Phys. Chem. A 2002; 106: 5288

11 Paddon-Row MN, Cotsaris E, Patney HK. Tetrahedron 1986; 42: 1779

12a Roest MR, Verhoeven JW, Schuddeboom W, Warman JM, Lawson JM, Paddon-Row MN. J. Am. Chem. Soc. 1996; 118: 1762
12b Lawson JM, Paddon-Row MN. J. Chem. Soc., Chem. Commun. 1993; 1641

13 Warrener RN, Schultz AC, Butler DN, Wang S, Mahadevan IB, Russell RA. Chem. Commun. 1997; 1023

ACE = Alkene Cyloclobutene Epoxide:

14a Margetić D, Johnston MR, Tiekink ER. T, Warrener RN. Tetrahedron Lett. 1998; 39: 5277
14b Warrener RN, Margetić D, Sun G, Amarasekara AS, Foley P, Butler DN, Russell RA. Tetrahedron Lett. 1999; 40: 4111
14c Warrener RN, Margetić D, Amarasekara AS, Butler DN, Mahadevan IB, Russell RA. Org. Lett. 1999; 1: 199
14d Warrener RN, Margetić D, Amarasekara AS, Russell RA. Org. Lett. 1999; 2: 203
14e Butler DN, Hammond ML. A, Johnston MR, Sun G, Malpass JR, Fawcett J, Warrener RN. Org. Lett. 2000; 2: 721
14f Johnston MR, Latter MJ, Warrener RN. Aust. J. Chem. 2001; 54: 633

15 Schultz AC, Kelso LS, Johnston MR, Warrener RN, Keene FR. Inorg. Chem. 1999; 38: 4906

16a Warrener RN, Margetić D, Foley PJ, Butler DN, Winling A, Beales KA, Russell RA. Tetrahedron 2001; 57: 571
16b Trošelj P, Briš A, Murata Y, Margetić D. Struct. Chem. 2012; 23: 791

17 Corsaro A, Librando V, Chiacchio U, Pistara V. Tetrahedron 1996; 52: 13027
18 Hojo M, Aihara H, Ito H, Hosomi A. Tetrahedron Lett. 1996; 37: 9241
19 Brown P, Cookson RC. Tetrahedron 1968; 24: 2551
20 Margetić D, Russell RA, Warrener RN. Org. Lett. 2000; 2: 4003
21 Fifth International Electronic Conference on Synthetic Organic Chemistry, (ECSOC-5), Sept. 1–30, 2001 [CD-ROM edition ISBN 3-906980-06-5]. Kappe O, Merino P, Marzinzik A, Wennemers H, Wirth T, Vanden Eynde J.-J, Lin S.-K. MDPI; Basel: 2001. article 37
22 Butler DN, Barrette A, Snow RA. Synth. Commun. 1975; 5: 101

23a Seitz G, Wassmuth H. Chem.-Ztg. 1988; 112: 80
23b Chambers WJ, Coffman DD. J. Org. Chem. 1961; 26: 4410

24a Warrener RN, Elsey GM, Maksimović L, Johnston MR, Kennard CH. L. Tetrahedron Lett. 1995; 36: 7753
24b Warrener RN, Butler DN, Liao WY, Pitt IG, Russell RA. Tetrahedron Lett. 1991; 32: 1889
24c Margetić D, Eckert-Maksić M, Trošelj P, Marinić Ž. J. Flourine Chem. 2010; 131: 408
24d Trošelj P, Margetić D, Đilović I, Matković-Čalogović D. J. Heterocycl. Chem. 2013; 50: 83
24e Margetić D, Trošelj P, Johnston MR. Mini-Rev. Org. Chem. 2011; 8: 49

25a Johnston MR, Gunter MJ, Warrener RN. Tetrahedron 2002; 58: 3445
25b Warrener RN, Schultz AC, Johnston MR, Gunter MJ. J. Org. Chem. 1999; 64: 4218

26 Warrener RN, Wang S, Russell RA, Gunter MJ. Synlett 1997; 47

27a Bell TD. M, Ghiggino KP, Jolliffe KA, Ranasinghe MG, Langford SJ, Shephard MJ, Paddon-Row MN. J. Phys. Chem. A 2002; 106: 10079
27b Guldi DM, Luo C, Swartz A, Gómez JL, Segura JL, Martin N. J. Phys. Chem. A 2004; 108: 455
27c Ramos AM, Meskers SC. J, van Hal PA, Knol J, Hummelen JC, Janssen RA. J. J. Phys. Chem. A 2003; 107: 9269
27d Jolliffe KA, Langford SJ, Ranasinghe MG, Shephard MJ, Paddon-Row MN. J. Org. Chem. 1999; 64: 1238

28a Gust D. Acc. Chem. Res. 2001; 34: 40
28b Head NJ, Thomas J, Shephard MJ, Paddon-Row MN, Bell TD. M, Cabral NM, Ghiggino KP. J. Photochem. Photobiol. A 2000; 133: 105
28c Lawson JM, Craig DC, Oliver AM, Paddon-Row MN. Tetrahedron 1995; 51: 3841
28d Dixon IM, Collin J.-P, Sauvage J.-P, Flamigni L. Inorg. Chem. 2001; 40: 5507
28e D’Souza F, Deviprasad GR, Zandler ME, El-Khouly ME, Fujitsuka M, Ito O. J. Phys. Chem. A 2003; 107: 4801
28f Akasaka T, Mutai T, Otsuki J, Araki K. Dalton Trans. 2003; 1537
28g Larkina EA, Luzgina VN, Evstigneeva RP. Russ. J. Bioorg. Chem. 2002; 28: 322

29 This result indicated the advantage of anthracene as dipolarophile since multiple cycloadditions of CE-11 on ninhydrin failed. Margetić, D.; Mann, D. A.; Butler, D. N.; Warrener, R. N. unpublished results.

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