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DOI: 10.1055/a-1817-0882
DBU- and DABCO-Promoted Selective Access to 2,5-Diarylnitrobenzoates and Cyclohexenones via One-Pot Reactions
The authors thank SERB-DST research grant (CRG/2018/001111), Government of India for generous financial support and SIC facility, Indian Institute of Technology (IIT) Indore.
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Abstract
Remarkable organobase-controlled selective synthesis of a wide breadth of valuable 2,5-diaryl-4-nitrobenzoates and 1-hydroxy-4-oxocyclohexencarboxylates bearing a tetrasubstituted stereogenic carbon is reported. This one-pot cyclization reaction operates between a bunch of 3-nitroallylarenes and β,γ-unsaturated α-ketocarbonyls by carefully choosing DBU or DABCO as an organobase under aerobic conditions. Notably, as a nucleophilic base, DABCO favors the Nef reaction over the dehydration–aerial oxidation process, aiming for unexpected cyclohexanone architectures. Moreover, this operationally simple technique holds a few positive qualities: good yields with diastereoselectivities (dr ≤ 91:9), broad substrate scope, no added oxidant, excellent functional group compatibility, 100% carbon-economical, etc. Furthermore, the obtained 4-nitrobenzoate framework has been utilized for the synthesis of a range of valuable compounds such as 2-phenylcarbazole-3-carboxylate, 3-bromoaniline derivative, and 2,5-diphenylbenzoic acid, among others.
Key words
one-pot - organobase-controlled reactions - 3-nitroallylarenes - 2,5-diarylnitrobenzoates - cyclohexenonesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1817-0882. Included are experimental details, characteristic data, 1H and 13C NMR spectra of products.
- Supporting Information
Publication History
Received: 01 February 2022
Accepted after revision: 05 April 2022
Accepted Manuscript online:
05 April 2022
Article published online:
09 May 2022
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Notes and References
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- 21 Representative Procedure for the Synthesis of 4aaTo a stirred solution of 1a (32.63 mg, 0.2 mmol) and 2a (51.1 mg, 0.25 mmol) in dry toluene (1.0 mL) was added DABCO (0.02 mmol, 10 mol%) at room temperature for 30 min under air. Afterwards, DABCO (0.28 mmol, 1.4 equiv) was added to the above solution at 60 °C in an open atmosphere for 15 h. Then, the reaction mixture was quenched with a very diluted HCl, followed by the extraction using EtOAc (3 × 10 mL) and dried over Na2SO4. After evaporation of the solvent, the crude residue was purified through column chromatography over silica gel using ethyl acetate/hexane (1:15) as a mixture of solvent to provide a pure colorless solid 4aa (45.1 mg, 67% yield); mp 115–117 °C; dr = 91:9; yield 67%. 1H NMR (500 MHz, CDCl3): δ = 7.53 (dd, J = 5.3, 3.3 Hz, 2 H), 7.38–7.35 (m, 5 H), 7.31–7.29 (m, 1 H), 7.22 (d, J = 7.1 Hz, 2 H), 6.40 (s, 1 H), 4.33 (dd, J = 13.5, 4.3 Hz, 1 H), 4.08–4.02 (m, 1 H), 3.95–3.90 (m, 2 H), 2.89 (t, J = 13.4 Hz, 1 H), 2.32 (dd, J = 13.3, 4.4 Hz, 1 H), 0.80 (t, J = 7.1 Hz, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 198.2, 175.1, 154.4, 138.2, 137.5, 129.6, 129.4, 129.0, 128.79, 128.78, 127.4, 126.7, 74.8, 63.0, 48.3, 43.7, 13.5 ppm. HRMS (ESI): m/z calcd for C21H20NaO4 [M + Na]+: 359.1259; found: 359.1266.
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