Abstract
Many medium ring-sized heterocyclic motifs are found in naturally occurring compounds of significant biological activity which led to the investigation of the biological activity of simpler heterocyclic compounds accommodating these ring systems. Therefore, the development of newer synthetic methodologies to access such ring systems has remained an important activity over the last few decades. However, common methods of their synthesis are usually associated with thermodynamic disadvantages. Many metal-mediated transformations e.g., Heck reaction, Suzuki reaction, etc. tend to overcome some of these effects but at the cost of environmental disadvantages. In recent years, several green chemical techniques have found useful applications in the synthesis of such ring systems. In particular, the use of microwave technology has provided better opportunities. The present review attempts to highlight many synthetic approaches developed for the synthesis of such heterocyclic scaffolds of pharmacological interest involving condensation reaction, coupling reaction, Multi-component reaction, Cyclo-addition reaction, Dipolar cycloaddition reaction, etc. An emphasis has also been given on the distinct advantages offered by microwave application over classical approaches, wherever such knowledge is available.
Keywords: Microwave, oxepine, azepine, diazepine, oxazepine, thiazepine, bioactive molecules, condensation reaction, multicomponent reaction, metal-catalyzed reaction.
Graphical Abstract
[http://dx.doi.org/10.1002/9783527634880]
[http://dx.doi.org/10.1002/9783527634880]
[http://dx.doi.org/10.1016/j.tet.2012.05.081]
[http://dx.doi.org/10.1021/jm00351a012] [PMID: 6982340]
[http://dx.doi.org/10.1021/jm00349a018] [PMID: 7108902]
[http://dx.doi.org/10.1021/jm00014a024] [PMID: 7629811]
[http://dx.doi.org/10.1159/000026605] [PMID: 10474065]
[http://dx.doi.org/10.1351/pac199971112039]
[http://dx.doi.org/10.1016/S0031-9422(00)90742-8]
[http://dx.doi.org/10.1021/jo00105a052]
[http://dx.doi.org/10.7164/antibiotics.50.325] [PMID: 9186558]
[http://dx.doi.org/10.1021/np070010e] [PMID: 17480099]
(b) Kraus, G.A.; Thite, A.; Liu, F. Intramolecular radical cyclizations onto quinones. A direct synthesis of Bauhinoxepin J. Tetrahedron Lett., 2009, 50, 5303-5304.
[http://dx.doi.org/10.1016/j.tetlet.2009.06.143]
[http://dx.doi.org/10.1016/S0040-4039(01)81724-X]
[http://dx.doi.org/10.1021/np058075+] [PMID: 16562827]
[http://dx.doi.org/10.1055/s-2008-1072719]
[http://dx.doi.org/10.1021/ja043898r] [PMID: 15631454]
[http://dx.doi.org/10.1021/ja064742p] [PMID: 17090008]
[http://dx.doi.org/10.1021/cr050045o] [PMID: 17212476]
[http://dx.doi.org/10.1016/j.tetlet.2009.09.117]
[http://dx.doi.org/10.1021/jm00179a005] [PMID: 6103962]
[http://dx.doi.org/10.1248/cpb.52.262] [PMID: 14758015]
[http://dx.doi.org/10.1016/j.bmc.2019.115122] [PMID: 31623970]
[http://dx.doi.org/10.1021/jm00004a016] [PMID: 7861418]
[http://dx.doi.org/10.1016/j.compbiomed.2019.05.023] [PMID: 31173941]
[http://dx.doi.org/10.1021/acs.jmedchem.8b01200] [PMID: 30351933]
[http://dx.doi.org/10.1080/00304940409458673]
[http://dx.doi.org/10.1021/ol302371s] [PMID: 22984846]
[http://dx.doi.org/10.3390/molecules181214797] [PMID: 24352054]
[http://dx.doi.org/10.1021/jo902117e] [PMID: 20000660]
[http://dx.doi.org/10.1016/S0040-4039(02)01806-3]
(b) Chattopadhyay, S.K.; Maity, S.; Pal, B.K. Combined multiple claisen rearrangement and ring-closing metathesis as a route to naphthalene, anthracene and anthracycline ring systems Chem. Lett, 2003, 1190-1191.
[http://dx.doi.org/10.1246/cl.2003.1190]
(c) Chattopadhyay, S.K.; Ray, S.P.; Ghosh, D.; Biswas, G. Synthesis of oxepine-, oxocine- and azepine-annulated carbazole derivatives by combined claisen rearrangement and diene/enyne metathesis. Tetrahedron Lett, 2006, 47, 6895-6898.
[http://dx.doi.org/10.1016/j.tetlet.2006.07.045]
(d) Chattopadhyay, S.K.; Biswas, T.; Maity, S. Sequential double claisen rearrangement and two-directional ring-closing metathesis as a route to various benzofused bis-oxepin and bis-oxocin derivatives Synlett, 2006, 2211-2214.
[http://dx.doi.org/10.1055/s-2006-950398]
(e) Chattopadhyay, S.K.; Biswas, T.; Neogi, K. Synthesis of polycyclic coumarin derivatives by combined claisen rearrangement, ring-closing metathesis, and diels - alder reaction Chem. Lett, 2006, 35, 376-377.
[http://dx.doi.org/10.1246/cl.2006.376]
[http://dx.doi.org/10.1016/S0968-0896(01)00112-2] [PMID: 11504632]
(b) Grunewald, G.L.; Caldwell, T.M.; Li, Q.; Criscione, K.R. Synthesis and evaluation of 4-fluoro-8-substituted-2,3,4,5-tetrahydro- 1H-2-benzazapines as selective inhibitors of phenylethanolamine N-methyltransferase versus the α(2)-adrenoceptor. J. Med. Chem, 2001, 44(17), 2849-2856.
[http://dx.doi.org/10.1021/jm010147g] [PMID: 11495596]
(c) Ersmark, K.; Feierberg, I.; Bjelic, S.; Hamelink, E.; Hackett, F.; Blackman, M.J.; Hultén, J.; Samuelsson, B.; Aqvist, J.; Hallberg, A. Potent inhibitors of the Plasmodium falciparum enzymes plasmepsin I and II devoid of cathepsin D inhibitory activity. J. Med. Chem., 2004, 47(1), 110-122.
[http://dx.doi.org/10.1021/jm030933g] [PMID: 14695825]
[http://dx.doi.org/10.1074/jbc.M409740200] [PMID: 15513918]
(b) Kulanthaivel, P.; Hallock, Y.F.; Boros, C.; Hamilton, S.M.; Janzen, W.P.; Ballas, L.M.; Loomis, C.R.; Jiang, J.B.; Katz, B.; Steiner, J.R.; Clardy, J. Balanol: a novel and potent inhibitor of protein kinase C from the fungus Verticillium balanoides. J. Am. Chem. Soc., 1993, 115, 6452-6453.
[http://dx.doi.org/10.1021/ja00067a087]
[http://dx.doi.org/10.3762/bjoc.9.327] [PMID: 24454570]
[http://dx.doi.org/10.1073/pnas.98.4.2089] [PMID: 11172080]
[http://dx.doi.org/10.1021/jm0709034] [PMID: 18095642]
[http://dx.doi.org/10.1080/00397910008087389]
[http://dx.doi.org/10.1016/j.tet.2017.06.060]
[http://dx.doi.org/10.1016/S0040-4020(01)82334-6]
[http://dx.doi.org/10.1016/j.tet.2008.10.072]
[http://dx.doi.org/10.1002/ejoc.200600680]
[http://dx.doi.org/10.1002/ejoc.200801175]
[http://dx.doi.org/10.1021/jo100859y] [PMID: 20575586]
[http://dx.doi.org/10.1021/jo200251q] [PMID: 21391618]
[http://dx.doi.org/10.1021/ol071079g] [PMID: 17608431]
[http://dx.doi.org/10.1021/ol050806+] [PMID: 15957931]
[http://dx.doi.org/10.1016/j.tet.2007.01.063]
[http://dx.doi.org/10.1002/chem.200700177] [PMID: 17508369]
[http://dx.doi.org/10.1016/j.ejmech.2015.05.035] [PMID: 26067208]
[http://dx.doi.org/10.1021/jm100652h] [PMID: 20857909]
[http://dx.doi.org/10.1517/17425250802670482] [PMID: 19199377]
[http://dx.doi.org/10.2298/JSC150116013B]
[http://dx.doi.org/10.1016/S0065-2725(08)60830-2]
[http://dx.doi.org/10.1021/jm100739n] [PMID: 21049954]
[http://dx.doi.org/10.1023/B:COHC.0000037319.75957.fb]
[http://dx.doi.org/10.1016/j.catcom.2004.10.009]
[http://dx.doi.org/10.1002/jhet.5570440431]
[http://dx.doi.org/10.1016/S0040-4039(01)00155-1]
[http://dx.doi.org/10.1039/c1nj20551j]
[http://dx.doi.org/10.21577/0103-5053.20180031]
[http://dx.doi.org/10.1039/C6NJ04013F]
[http://dx.doi.org/10.1039/C3GC41898G]
[http://dx.doi.org/10.1134/S1066362216040123]
[http://dx.doi.org/10.1039/c2ob07063d] [PMID: 22371225]
[http://dx.doi.org/10.7598/cst2013.287]
[http://dx.doi.org/10.1016/j.tetlet.2011.02.042]
[http://dx.doi.org/10.1016/j.tetlet.2011.07.131]
[http://dx.doi.org/10.1016/j.tetlet.2009.09.107] [PMID: 20160922]
[http://dx.doi.org/10.1039/p19790001656]
[http://dx.doi.org/10.3892/or_00001011] [PMID: 21042745]
(b) Keating, G.M. Loxapine inhalation powder: a review of its use in the acute treatment of agitation in patients with bipolar disorder or schizophrenia. CNS Drugs, 2013, 27(6), 479-489.
[http://dx.doi.org/10.1007/s40263-013-0075-9] [PMID: 23740380]
[http://dx.doi.org/10.1021/jm3007933] [PMID: 23394126]
[http://dx.doi.org/10.1046/j.1365-2125.2003.01888.x] [PMID: 12968984]
[PMID: 8105359]
[http://dx.doi.org/10.1111/j.1476-5381.2010.00884.x] [PMID: 20718741]
[http://dx.doi.org/10.1016/j.tetlet.2011.06.029]
[http://dx.doi.org/10.1007/s11030-009-9223-z] [PMID: 20157778]
[http://dx.doi.org/10.1021/cr0509410] [PMID: 17451275]
[http://dx.doi.org/10.1039/b815879g] [PMID: 19156323]
[http://dx.doi.org/10.1073/pnas.0802982105] [PMID: 18579783]
[http://dx.doi.org/10.1016/j.tetlet.2009.05.028]
[http://dx.doi.org/10.14233/ajchem.2019.21716]
[http://dx.doi.org/10.1021/ja058451c] [PMID: 16536510]
[http://dx.doi.org/10.1002/ejoc.200300725]
[http://dx.doi.org/10.1007/s11030-014-9530-x] [PMID: 24894969]
[http://dx.doi.org/10.1021/acs.joc.6b01398] [PMID: 27517309]
[http://dx.doi.org/10.1016/j.bmc.2011.10.080] [PMID: 22137933]
[http://dx.doi.org/10.1021/jm070139l] [PMID: 17536796]
[http://dx.doi.org/10.1016/j.tetlet.2012.05.025]
[http://dx.doi.org/10.1016/j.ejmech.2010.11.043] [PMID: 21185625]
[http://dx.doi.org/10.1016/j.bmcl.2011.06.007] [PMID: 21763133]
[http://dx.doi.org/10.1021/cc1001023] [PMID: 20879738]
[http://dx.doi.org/10.1021/ol100035e] [PMID: 20178346]
[http://dx.doi.org/10.1039/C5OB01400J] [PMID: 26256838]
[http://dx.doi.org/10.1016/S0040-4020(01)00906-1]
(b) Bose, A.K.; Manhas, M.S.; Ganguly, S.N.; Sharma, A.H.; Banik, B.K. MORE chemistry for less pollution: applications for process development Synthesis, 2002, 1578-1591.
[http://dx.doi.org/10.1055/s-2002-33344]
(c) Caddick, S.; Fitzmaurice, R. Microwave enhanced synthesis Tetrahedron, 2009, 65, 3325-3355.
[http://dx.doi.org/10.1016/j.tet.2009.01.105]
(d) Kappe, C.O.; Dallinger, D. Controlled microwave heating in modern organic synthesis: highlights from the 2004-2008 literature. Mol. Divers., 2009, 13(2), 71-193.
[http://dx.doi.org/10.1007/s11030-009-9138-8] [PMID: 19381851]
[http://dx.doi.org/10.1039/B815717K PMID: 20419202]
bSaber, A.; Marzag, H.; Benhida, R.; Bougrin, K. Microwave-assisted cycloaddition reactions in carbo- and heterocyclic chemistry. Curr. Org. Chem., 2014, 18, 2139-2180.
[http://dx.doi.org/10.2174/1385272819666140407213427]
[http://dx.doi.org/10.1021/ar700238s] [PMID: 18419142]
[http://dx.doi.org/10.1039/c1cs15094d] [PMID: 21717007]
[http://dx.doi.org/10.1039/c1cs15094d] [PMID: 21717007]
(b) Sharma, A.; Appukkuttan, P.; Van der Eycken, E. Microwaveassisted synthesis of medium-sized heterocycles. Chem. Commun., 2012, 48, 1623-1637.
[http://dx.doi.org/10.2174/1385272819666140407213427]
(c) Chattopadhyay, S.K. Green synthetic approaches for medium ring-sized heterocycles of biological interest. In: Green Synthetic Approaches for Biologically relevant Heterocycles, Brahmachari, G. Elsevier, 2014; p. Chapter-XI
(d) Kaur, N.; Kishore, D; Van der , E. Microwave-assisted synthesis of seven- and higher-membered O-heterocycles Synth Commun, 2014, 44, 2739-2755.
(e) Sakhuja, R.; Bajaj, K.; Abdul Shakoor, S.M Microwaveassisted synthesis of benzo-fused seven-membered azaheterocycles Mini-Rev. Org. Chem, 2014, 11, 55-72.
(f) Demange, L.; Bougrin, K.; Benhida, R. Microwave-assisted syntheses of bioactive seven-membered, macro-sized heterocycles and their fused derivatives Molecules, 2016, 21, 1032-1078.
(g) Driowya, M.; Saber, A.; Marzag, H. Microwave-assisted synthesis of bioactive six-membered heterocycles and their fused analogues. Molecules, 2016, 21, 492-524.