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

Praveen Prakash; P. S. Aparna; E. Jijy; P. V. Santhini; Sunil Varughese; K. V. Radhakrishnan

doi:10.1055/s-0033-1340221

Synlett, Inhaltsverzeichnis

Synlett 2014; 25(2): 275-279
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

Praveen Prakash

^aOrganic Chemistry Section, National Institute for Interdisciplinary Science and Technology (CSIR), Trivandrum 695019, India Fax: +91(471)2491712 eMail: radhu2005@gmail.com

,

P. S. Aparna

^aOrganic Chemistry Section, National Institute for Interdisciplinary Science and Technology (CSIR), Trivandrum 695019, India Fax: +91(471)2491712 eMail: radhu2005@gmail.com

^bAcademy of Scientific and Innovative Research (AcSIR), New Delhi 110001, India

,

E. Jijy

^aOrganic Chemistry Section, National Institute for Interdisciplinary Science and Technology (CSIR), Trivandrum 695019, India Fax: +91(471)2491712 eMail: radhu2005@gmail.com

,

P. V. Santhini

^aOrganic Chemistry Section, National Institute for Interdisciplinary Science and Technology (CSIR), Trivandrum 695019, India Fax: +91(471)2491712 eMail: radhu2005@gmail.com

^bAcademy of Scientific and Innovative Research (AcSIR), New Delhi 110001, India

,

Sunil Varughese

^cInorganic Chemistry Section, National Institute for Interdisciplinary Science and Technology (CSIR), Trivandrum 695019, India

,

K. V. Radhakrishnan*

^aOrganic Chemistry Section, National Institute for Interdisciplinary Science and Technology (CSIR), Trivandrum 695019, India Fax: +91(471)2491712 eMail: radhu2005@gmail.com

^bAcademy of Scientific and Innovative Research (AcSIR), New Delhi 110001, India

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Abstract

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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.

Key words

rhodium - C–H activation - bicyclic olefin - cyclopentene - aza heteroaromatic

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Referenzen

References and Notes

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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 R_f = 0.65 (hexane–EtOAc, 5:5). IR (neat): ν_max = 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 R_f = 0.43 (hexane–EtOAc, 5:5); mp 163–165 °C. IR (neat): ν_max = 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

For recent reports on β-oxygen elimination, see:

24a Wang H, Schroder N, Glorius F. Angew. Chem. Int. Ed. 2013; 52: 5386
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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

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Supporting Information

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

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