Synlett 2017; 28(13): 1564-1569
DOI: 10.1055/s-0036-1589014
cluster
© Georg Thieme Verlag Stuttgart · New York

Iron-Catalyzed Aerobic Oxidation of (Alkyl)(aryl)azinylmethanes

Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp, Belgium   Email: bert.maes@uantwerpen.be
,
Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp, Belgium   Email: bert.maes@uantwerpen.be
,
Filip Lemière
Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp, Belgium   Email: bert.maes@uantwerpen.be
,
Kourosch Abbaspour Tehrani
Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp, Belgium   Email: bert.maes@uantwerpen.be
,
Bert U. W. Maes*
Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp, Belgium   Email: bert.maes@uantwerpen.be
› Author Affiliations
Further Information

Publication History

Received: 28 February 2017

Accepted after revision: 11 April 2017

Publication Date:
02 May 2017 (online)

Published as part of the Cluster Catalytic Aerobic Oxidations

Abstract

An iron-catalyzed aerobic oxidation of (alkyl)(aryl)azinylmethanes has been developed leading to tertiary alcohols in moderate to good yields. Hock rearrangement was identified as a major side reaction leading to a complex mixture of undesired products. Addition of thiourea sometimes allows inhibiting this side reaction and steers the reaction towards the desired products.

Supporting Information

 
  • References and Notes


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  • 16 Typical Procedure for Fe-Catalyzed Aerobic C–H Oxygenation of 1a A 10 mL vial was charged with FeCl2·4H2O (9.94 mg, 0.050 mmol), 2-(1-phenylethyl)pyridine (1a) (0.092 g, 0.5 mmol), salicylic acid (0.069 g, 0.500 mmol), and DMSO (1 mL). The vial was flushed for 10 s with O2, capped with an aluminum crimp cap with septum and stirred at 100 °C for 24 h with an O2 balloon through the septum. After cooling down to r.t., the content of the vial was transferred into a separation funnel and the vial was rinsed with CH2Cl2 (20 mL). Aqueous sat. NaHCO3 (10 mL) was added, and the organic phase was separated. The aqueous phase was extracted twice with CH2Cl2 (10 mL). The combined organic fractions were washed with brine (20 mL), dried on MgSO4, and filtered. Further purification was achieved by automated column chromatography (heptane–EtOAc) to give 1-phenyl-1-(pyridin-2-yl)ethanol (2a) in 88% yield. Characterization Data for 2a Colorless oil. ESI–HRMS: m/z calcd for C13H14NO [M + H]+: 200.1070; found: 200.1080. 1H NMR (400 MHz, CDCl3): δ = 8.51 (d, 1 H, J = 4.6 Hz), 7.62 (dt, 1 H, J = 7.8, 1.4 Hz), 7.47 (d, 2 H, J = 7.4 Hz), 7.34–7.25 (m, 3 H), 7.25–7.11 (m, 2 H), 5.80 (s, 1 H), 1.92 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 164.8 (C], 147.4 (CH), 147.2 (C), 136.9 (CH), 128.2 (CH), 127.0 (CH), 125.9 (CH), 122.0 (CH), 120.3 (CH), 75.1 (C), 29.3 (CH3). Characterization Data for 2m Colorless viscous oil. ESI–HRMS: m/z calcd for C22H20NO5 [M + H]+: 378.1336; found: 378.1342. 1H NMR (400 MHz, CDCl3): δ = 8.58 (d, 1 H, J = 4.5 Hz), 7.65 (dt, 1 H, J = 7.7, 1.3 Hz), 7.29 (d, 4 H, J = 8.6 Hz), 7.26–7.21 (m, 1 H), 7.12 (d, 1 H, J = 7.9 Hz), 7.02 (d, 4 H, J = 8.6 Hz), 6.29 (br s, 1 H), 2.28 (s, 6 H). 13C NMR (100 MHz, CDCl3): δ = 169.3 (C), 162.7 (C), 150.0 (C), 147.8 (CH), 143.4 (C), 136.6 (CH), 129.3 (CH), 122.9 (CH), 122.6 (CH), 121.0 (CH), 80.2 (C), 21.2 (CH3).