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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
Further Information
Publication History
Received: 29 September 2013
Accepted after revision: 14 October 2013
Publication Date:
06 December 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
-
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- 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.
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- 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: