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Synlett 2014; 25(2): 275-279
DOI: 10.1055/s-0033-1340221
DOI: 10.1055/s-0033-1340221
letter
Rhodium(III)-Catalyzed C–H Activation of Phenylazoles toward C–N Bond Cleavage of Diazabicyclic Olefins: A Facile Access to Mono- and Biscyclopentenyl-Functionalized Aza-Heteroaromatics
Weitere Informationen
Publikationsverlauf
Received: 29. September 2013
Accepted after revision: 14. Oktober 2013
Publikationsdatum:
06. Dezember 2013 (online)
Abstract
A [RhCl2Cp*]2-catalyzed stereoselective C–N bond cleavage of diazabicyclic olefins via C–H activation of phenylazoles in the presence of an acetate source is described. The developed method provides an easy access to biologically significant mono- and biscyclopentenyl- and alkylidenecyclopentenyl-functionalized aza heteroaromatics.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
-
References and Notes
- 1a Thomas GL, Johannes CW. Curr. Opin. Chem. Biol. 2011; 15: 516
- 1b Joule JA, Mills K. Heterocyclic Chemistry . Wiley Blackwell; Oxford: 2010. 5th ed
- 1c Comprehensive Heterocyclic Chemistry III . Katritzky AR, Ramsden CA, Scriven EF. V, Taylor RJ. K. Pergamon; Oxford: 2008; and references cited therein
- 1d Moonen K, Laureyn I, Stevens CV. Chem. Rev. 2004; 104: 6177
- 1e Eicher T, Hauptmann S. The Chemistry of Heterocycles . Wiley-VCH; Weinheim: 2003
- 2a Dembitsky VM, Gloriozova TA, Poroikov VV. Mini-Rev. Med. Chem. 2005; 5: 319
- 2b Jin Z. Nat. Prod. Rep. 2005; 22: 196 ; and references cited therein
- 2c Grimmett MR In Comprehensive Heterocyclic Chemistry II . Vol. 3. Elsevier; Oxford: 1996: 77
- 3a Boiami M, Gonzalez M. Mini-Rev. Med. Chem. 2005; 5: 409
- 3b Figueiras A, Sarraguca JM. G, Carvalho RA, Pais AA. C. C, Veiga FJ. B. Pharm. Res. 2007; 24: 377
- 3c Welsch ME, Snyder SA, Stockwell BR. Curr. Opin. Chem. Biol. 2010; 14: 1
- 3d Dasari M, Lee S, Sy J, Kim D, Lee S, Brown M, Davis M, Murthy N. Org. Lett. 2010; 12: 3300
- 4a Elguero J In Comprehensive Heterocyclic Chemistry . Vol. 5. Katritzky AR, Rees CW, Scriven EF. V. Pergamon; Oxford: 1996
- 4b Elguero J, Goya P, Jagerovic N, Silva AM. S. Targets Heterocycl. Syst. 2002; 6: 52
- 4c Kumar GG, Vikas K, Vinod K. Res. J. Chem. Environ. 2011; 15: 90
- 4d Padwa A, Bur S. Chem. Rev. 2004; 104: 2401 ; and references cited therein
- 5a Lillelund VH, Jensen HH, Liang X, Bols M. Chem. Rev. 2002; 102: 515
- 5b Trost BM, Van Vranken DL. J. Am. Chem. Soc. 1993; 115: 444
- 5c Ogawa S, Morikawa T. Eur. J. Org. Chem. 2000; 1759
- 5d Puder C, Krastel P, Zeeck A. J. Nat. Prod. 2000; 63: 1258
- 5e Revial G, Jahin I, Pfau M. Tetrahedron: Asymmetry 2000; 11: 4975
- 6a Wencel-Delord J, Glorius F. Nat. Chem. 2013; 5: 369
- 6b Zhao D, Shi Z, Glorius F. Angew. Chem. Int. Ed. 2013; 52 in press; DOI: 10.1002/anie.201306098
- 6c Patureau FW, Wencel-Delord J, Glorius F. Aldrichimica Acta 2012; 45: 31
- 6d Song G, Wang F, Li X. Chem. Soc. Rev. 2012; 41: 3651
- 6e Engle KM, Mei T.-S, Wasa M, Yu J.-Q. Acc. Chem. Res. 2012; 45: 788
- 6f Kuhl N, Hopkinson MN, Wencel-Delord J, Glorius F. Angew. Chem. Int. Ed. 2012; 51: 10236
- 6g Sun C.-L, Li B.-J, Shi Z.-J. Chem. Rev. 2011; 111: 1293
- 6h Satoh T, Miura M. Chem. Eur. J. 2010; 16: 11212
- 6i Ackermann L. Chem. Rev. 2011; 111: 1315
- 6j Colby DA, Bergman RG, Ellman JA. Chem. Rev. 2010; 110: 624
- 7a Umeda N, Tsurugi H, Satoh T, Miura M. Angew. Chem. Int. Ed. 2008; 47: 4019
- 7b Umeda N, Hirano K, Satoh T, Miura M. J. Org. Chem. 2009; 74: 7094
- 7c Li X, Zhao M. J. Org. Chem. 2011; 76: 8530
- 7d Morimoto K, Hirano K, Satoh T, Miura M. Org. Lett. 2010; 9: 2068
- 7e Hashimoto Y, Ortloff T, Hirano K, Satoh T, Bolm C, Miura M. Chem. Lett. 2012; 41: 151
- 7f Ma W, Graczyk K, Ackermann L. Org. Lett. 2012; 24: 6318
- 7g Huang J.-R, Zhang Q.-R, Qu C.-H, Sun X.-H, Dong L, Chen Y.-C. Org. Lett. 2013; 8: 1878
- 7h Ackermann L, Novak P, Vicente R, Hofmann N. Angew. Chem. Int. Ed. 2009; 48: 6045
- 7i Chatani N, Inoue S, Yokota K, Tatamidani H, Fukumoto Y. Pure Appl. Chem. 2010; 82: 1443
- 8 Umeda N, Hirano K, Satoh T, Shibata N, Sato H, Miura M. J. Org. Chem. 2011; 76: 13
- 9 Hashimoto Y, Ueyama T, Fukutani T, Hirano K, Satoh T, Miura M. Chem. Lett. 2011; 40: 1165
- 10 Arockiam PB, Fischmeister C, Bruneau C, Dixneuf PH. Green Chem. 2011; 13: 3075
- 11 Li B, Devaraj K, Darcel C, Dixneuf PH. Green Chem. 2012; 14: 2706
- 12a Storsberg J, Nandakumar MV, Sankaranarayanan S, Kaufmann DE. Adv. Synth. Catal. 2001; 343: 177
- 12b Yao ML, Adiwidjaja G, Kaufmann DE. Angew. Chem. Int. Ed. 2002; 41: 3375
- 13a Palais L, Bournaud C, Micouin L, Alexakis A. Chem. Eur. J. 2010; 16: 2567
- 13b Bournaud C, Chung F, Luna AP, Pasco M, Errasti G, Lecourt T, Micouin L. Synthesis 2009; 869
- 13c Palais L, Mikhel IS, Bournaud C, Micouin L, Falciola CA, Vuagnoux-d’Augustin M, Rosset S, Bernardinelli G, Alexakis A. Angew. Chem. Int. Ed. 2007; 46: 7462
- 13d Bournaud C, Falciola C, Lecourt T, Rosset S, Alexakis A, Micouin L. Org. Lett. 2006; 8: 3581
- 14a Bexrud J, Lautens M. Org. Lett. 2010; 12: 3160
- 14b Martins A, Lemouzy S, Lautens M. Org. Lett. 2009; 11: 181
- 14c Panteleev J, Menard F, Lautens M. Adv. Synth. Catal. 2008; 350: 2893
- 14d Menard F, Lautens M. Angew. Chem. Int. Ed. 2008; 47: 2085
- 14e Menard F, Weise CF, Lautens M. Org. Lett. 2007; 9: 5365
- 15a Crotti S, Bertolini F, Macchia F, Pineschi M. Adv. Synth. Catal. 2009; 351: 869
- 15b Crotti S, Bertolini F, Macchia F, Pineschi M. Chem. Commun. 2008; 312
- 15c Pineschi M, Moro FD, Crotti P, Macchia F. Org. Lett. 2005; 7: 3605
- 16a Radhakrishnan KV, Sajisha VS, Anas S, Krishnan KS. Synlett 2005; 2273
- 16b Sajisha VS, Radhakrishnan KV. Adv. Synth. Catal. 2006; 348: 924
- 16c John J, Sajisha VS, Mohanlal S, Radhakrishnan KV. Chem. Commun. 2006; 3510
- 16d Anas S, John J, Sajisha VS, John J, Rajan R, Suresh E, Radhakrishnan KV. Org. Biomol. Chem. 2007; 5: 4010
- 16e John J, Anas S, Sajisha VS, Viji S, Radhakrishnan KV. Tetrahedron Lett. 2007; 48: 7225
- 16f Sajisha VS, Anas S, John J, Radhakrishnan KV. Synlett 2009; 2885
- 16g John J, Adarsh B, Radhakrishnan KV. Tetrahedron 2010; 66: 1383
- 17 Bhanu Prasad BA, Buechele AE, Gilbertson SR. Org. Lett. 2010; 12: 5422
- 18a John J, Indu U, Suresh E, Radhakrishnan KV. J. Am. Chem. Soc. 2009; 131: 5042
- 18b Prakash P, Jijy E, Preethanuj P, Pihko PM, Sarath Chand S, Radhakrishnan KV. Chem. Eur. J. 2013; 19: 10473
- 18c Radhakrishnan KV, Jijy E, Prakash P, Shimi M, Pihko PM, Joseph N. Chem. Commun. 2013; 49: 7349
- 18d Sarath Chand S, Jijy E, Prakash P, Szymoniak J, Preethanuj P, Dhanya BP, Radhakrishnan KV. Org. Lett. 2013; 15: 3338
- 19 Typical Experimental Procedure for 3aa and 4aa A mixture of bicyclic olefin 2a (0.2083 mmol, 1.75 equiv), 2-phenylimidazole (0.1191 mmol, 1.0 equiv), [RhCl2Cp*]2 (0.0029 mmol, 2.5 mol%), and Cu(OAc)2·H2O (0.1338 mmol, 1.5 equiv) were weighed in a Schlenk tube and degassed for 10 min. Anhydrous MeCN (2 mL) was added, and the reaction mixture was purged with argon and allowed to stir at 80 °C for 12 h. The solvent was evaporated in vacuo, and the residue was purified with column chromatography (silica gel, 100–200 mesh) using an EtOAc–hexane mixture. Mono- and biscyclopentenyl-functionalized aza heteroaromatics were obtained in 48% and 39% yields, respectively.
- 20 Spectral Data of Compound 3aa Rf = 0.65 (hexane–EtOAc, 5:5). IR (neat): νmax = 3284, 3059, 2981, 2929, 2863, 1716, 1634, 1593, 1472, 1416, 1380, 1273, 1245, 1217, 1165, 1130, 1098, 1059, 950, 863, 809, 763, 664, 661, 557 cm–1. 1H NMR (500 MHz, CDCl3, TMS): δ = 10.71–10.17 (m, 2 H), 7.41–7.33 (m, 1 H), 7.16–7.03 (m, 5 H), 5.81 (s, 1 H), 5.45 (s, 1 H), 5.04–4.86 (m, 2 H), 4.19–4.17 (m, 2 H), 3.92–3.72 (m, 2 H), 2.59–2.56 (m, 2 H), 1.32–1.23 (m, 3 H), 1.01–0.77 (m, 3 H). 13C NMR (125 MHz, CDCl3): δ = 156.8, 156.6, 145.7, 141.8, 141.6, 133.9, 133.7, 129.6, 129.3, 129.1, 128.3, 126.6, 117.1, 69.4, 61.8, 61.7, 47.2, 34.4, 14.6, 14.2. ESI-HRMS: m/z calcd for C20H24N4O4 [M + Na]: 407.16952; found: 407.17032.
- 21 Spectral Data of Compound 4aa Rf = 0.43 (hexane–EtOAc, 5:5); mp 163–165 °C. IR (neat): νmax = 3341, 2963, 2925, 2856, 1746, 1632, 1590, 1528, 1405, 1371, 1313, 1269, 1155, 1109, 1028, 757, 719, 665, 610, 557 cm–1. 1H NMR (500 MHz, CDCl3, TMS): δ = 10.78 (br s, 1 H), 7.42–7.37 (m, 1 H), 7.20–7.16 (m, 3 H), 7.00 (m, 1 H), 5.75 (s, 2 H), 5.44 (s, 2 H), 4.82–4.54 (m, 2 H), 4.11–3.78 (m, 10 H), 2.62–2.47 (m, 4 H), 1.25–1.21 (m, 12 H). 13C NMR (125 MHz, CDCl3): δ = 156.7, 156.2, 155.8, 144.9, 143.9, 133.5, 132.7, 131.3, 130.0, 129.5, 128.5, 128.2, 125.7, 116.3, 71.1, 69.1, 62.1, 61.7, 49.1, 35.1, 29.7, 14.4, 14.3, 14.1. ESI-HRMS: m/z calcd for C31H40N6O8 [M + 1]: 625.29076; found: 625.29822.
- 22 CCDC Number: 952086.
- 23 Prakash P, Jijy E, Shimi M, Aparna PS, Suresh E, Radhakrishnan KV. RSC Adv. 2013; 3: 19933
- 24a Wang H, Schroder N, Glorius F. Angew. Chem. Int. Ed. 2013; 52: 5386
- 24b Wang H, Beiring B, Yu D-G, Collins KD, Glorius F. Angew. Chem. Int. Ed. 2013; 52 in press; DOI: 10.1002/anie.201306754
- 25 When the present manuscript was ready for submission, a similar report appeared in Chemical Science as accepted manuscript. See: Cui S, Zhang Y, Qi W. Chem. Sci. 2013; in press; DOI: 10.1039/C3SC52524D
For recent reports on C–H activation, see:
For recent reports on β-oxygen elimination, see: