Synlett
DOI: 10.1055/s-0039-1691497
cluster
© Georg Thieme Verlag Stuttgart · New York

Aza-Morita–Baylis–Hillman Reaction with Vinyl-oxadiazoles: An Expeditious Approach to Access New Heterocyclic Arrangements

André Capretz-Agy
,
Fábio S. Fernandes
,
Manoel T. Rodrigues Jr.
,
Caroline Conti
,
São Paulo Foundation for Science (FAPESP, Grant No. 2013/07600-3, 2018/02611-0, and 2016/23005-6 to F.C and F.S.F.), Coordenacão de Aperfeiçoamento de Pessoal de Nivel Superior–Brasil (CAPES, Finance Code 001 to M.T.R.Jr. and A.A.C), and Brazilian National Council for Science and Development (CNPq, Processes No. 422890/2016-2 and 301330/2018-2).
Further Information

Publication History

Received: 16 October 2019

Accepted after revision: 09 November 2019

Publication Date:
25 November 2019 (online)


Published as part of the ISySyCat2019 Special Issue

Abstract

In this communication, we disclosed a new aza-MBH reaction in which traditional nucleophilic partners of these reactions (e.g., acrylates, nitroolefins or enones) were replaced by vinyl-1,2,4-oxadiazoles. Thus, the aza-MBH reaction between 5-aryl-3-vinyl-1,2,4-oxadiazoles and N-sulfonylimines, catalyzed by the mixture DABCO/AcOH, provides a class of new adduct in yields varying from 31% up to 93% in reaction times from 30 minutes to 24 hours. Due to the biological activities and technological applications associated with the 1,2,4-oxadiazole motifs, this new class of heterocycles offers great synthetic and commercial potentiality.

Supporting Information

 
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  • 25 General Procedure for the Synthesis of 1,2,4-Oxadiazole 1d25 trans-β-Nitrostyrene 1 (2.0 mmol) was added to a mixture of TfOH (3.5 mL), CH2Cl2 (3.0 mL), and benzene (3.0 mmol) at –40 °C. After stirring at –40 °C for 1.5 h, the reaction mixture was poured at once into acrylonitrile (9.0 mmol) cooled to –30 °C. The resulting solution was heated to –20 °C and stirred at this temperature for 30 min, then quenched with water (30 mL) and extracted with CHCl3 (3 × 30 mL). The combined organic phases were washed three times with water (40 mL) and dried with Na2SO4. The solvent was evaporated under the reduced pressure, and the residue was purified by chromatography column (hexane/EtOAc = 9:1); mp 53–55 °C. 1H NMR (250 MHz, CDCl3): δ = 7.53–7.27 (m, 10 H), 6.76 (dd, J = 17.7, 10.9 Hz, 1 H), 6.55 (dd, J = 17.7, 1.1 Hz, 1 H), 5.96 (dd, J = 10.9, 1.1 Hz, 1 H), 5.75 (s, 1 H). 13C NMR (63 MHz, CDCl3): δ = 174.57, 172.11, 139.71, 128.92, 128.80, 128.73, 127.36, 120.68, 48.80. HRMS (ESI-TOF): m/z calcd for C17H15N2O [M + H]+: 263.1179; found: 263.1189.
  • 26 General Procedure for the Synthesis of Aza-Morita–Baylis–Hilman Adducts 3a–p In a 2mL flask equipped with a magnetic stir bar, oxadiazole (0.29 mmol), imine (0.32 mmol), and DABCO (34 mg, 0.30 mmol) were added sequentially. The atmosphere of the flask was exchanged for N2, and then toluene (0.29 mL) and acetic acid (18 μL, 0.30 mmol) were added. The reaction was stirred at room temperature, and the time was specified for each substrate. After consumption of the starting material, as determined by TLC, the crude reaction was evaporated under reduced pressure. The residue was then purified by flash silica gel column chromatography (hexane/EtOAc = 9:1 to 7:3) to provide the aza-MBH adduct. N-{2-[3-(4-Methoxyphenyl)-1,2,4-oxadiazol-5-yl]-1-phenylprop-2-en-1-yl}benzenesulfonamide (3h) Purified by column chromatography (hexane/EtOAc = 8:2) to give 3h (100 mg, 0.22 mmol, 90%) as a white solid; mp 152–153 °C. 1H NMR (500 MHz, CDCl3): δ = 7.84 (d, J = 8.8 Hz, 2 H), 7.70 (d, J = 7.5 Hz, 2 H), 7.42 (t, J = 7.5 Hz, 1 H), 7.31 (t, J = 7.5 Hz, 2 H), 7.26–7.09 (m, 5 H), 6.90 (d, J = 8.8 Hz, 2 H), 6.22 (s, 1 H), 6.18 (d, J = 9.2 Hz, 1 H), 5.81 (s, 1 H), 5.53 (d, J = 9.2 Hz, 1 H), 3.79 (s, 3 H). 13C NMR (125 MHz, CDCl3): δ = 172.8, 168.1, 162.3, 140.5, 137.9, 132.9, 132.2, 129.2, 129.0, 128.8, 128.3, 127.3, 126.7, 126.3, 118.7, 114.4, 59.9, 55.6. HRMS (ESI-TOF): m/z calcd for C24H22N3O4S+ [M + H]+: 448.1326; found: 448.1311. N-{2-[3-(4-Methoxyphenyl)-1,2,4-oxadiazol-5-yl]-1-(4-nitrophenyl)prop-2-en-1-yl}benzenesulfonamide (3i) Purified by column chromatography (hexane/EtOAc = 8:2) to give 3i (99 mg, 0.20 mmol, 81%) as a yellow oil. 1H NMR (250 MHz, CDCl3): δ = 8.12 (d, J = 8.5 Hz, 2 H), 7.89 (d, J = 8.5 Hz, 2 H), 7.79 (dd, J = 8.2, 1.5 Hz, 2 H), 7.54 (dd, J = 8.2, 6.6 Hz, 3 H), 7.42 (t, J = 7.5 Hz, 2 H), 6.98 (d, J = 8.5 Hz, 2 H), 6.62 (d, J = 9.6 Hz, 1 H), 6.34 (s, 1 H), 5.92 (s, 1 H), 5.70 (d, J = 9.6 Hz, 1 H), 3.88 (s, 2 H). 13C NMR (63 MHz, CDCl3): δ = 172.14, 168.17, 162.49, 147.77, 145.23, 140.26, 133.31, 131.19, 127.79, 127.41, 127.20, 123.99, 118.29, 114.57, 59.65, 55.63. HRMS (ESI-TOF): m/z calcd for C24H21N4O6S+ [M + H]+: 493.1176; found: 493.1188. N-{[1-(4-Bromophenyl)-2-[3-(diphenylmethyl)-1,2,4-oxadiazol-5-yl]prop-2-en-1-yl}benzenesulfonamide (3m) Purified by column chromatography (hexane/EtOAc = 8:2 to 7:3) to give 3m (103 mg, 0.18 mmol, 93%) as a colorless oil. 1H NMR (250 MHz, CDCl3): δ = 7.56–7.43 (m, 3 H), 7.40–7.20 (m, 12 H), 7.18–7.04 (m, 4 H), 6.27–6.13 (m, 2 H), 5.88 (s, 1 H), 5.56 (s, 1 H), 5.49 (d, J = 9.7 Hz, 1 H). 13C NMR (63 MHz, CDCl3): δ = 172.48, 171.29, 140.14, 139.49, 138.98, 136.89, 132.77, 131.70, 131.40, 128.81, 128.76, 128.66, 128.64, 128.59, 128.26, 127.59, 127.42, 126.99, 126.42, 122.10, 59.58, 48.09. HRMS (ESI-TOF): m/z calcd for C30H25BrN3O3S+ [M + H]+: 586.0795; found: 586.0784.
  • 27 Iwabuchi Y, Nakatani M, Yokoyama N, Hatakeyama S. J. Am. Chem. Soc. 1999; 121: 10219 . Reactions were carried out with vinyl-oxadiazole 1a (0.16 mmol), N-sulfonylimine 2a (0.17 mmol), and β-isocupreidine (0.016 mmol)25 as chiral catalyst. So far the best conditions found led to an enantiomeric ratio of 68.5:31.5