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C–H allylation of N-aryl-tetrahydroisoquinolines by merging photoredox catalysis with iodide catalysis

Abstract

A dual catalytic system, combing visible light photoredox catalysis and iodide catalysis, has been developed for the functionalization of inert C–H bonds. By doing so, radical allylation reactions of N-aryl-tetrahydroisoquinolines (THIQs) were realized under extremely mild conditions, affording a wide variety of allyl-substituted THIQs in up to 78% yields.

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  51. General Procedure: In a 10 mL dry flask equipped with magnetic bar was charged with 1 (0.5 mmol, 1.0 equiv.) and Ir(bpy)2(dtbbpy)PF6 (2 mol%), 5 (0.75 mmol, 1.5 equiv.), KI (20 mol%), NaCO2CF3 (1.0 mmol, 2.0 equiv.) and MeCN (5 mL). The mixture was degassed via freeze-pump-thaw method (3 times) and then stirred under the irradiation of 7 W blue LEDs at room temperature for 12 h. The resultant mixture was filtered under vacuum to remove the solid. The filtrate was purified by flash chromatography on silica gel (petroleum ether/DCM=10:1) to afford the desired product 3. Analytical data of 1-allyl-2-phenyl-1,2,3,4-tetrahydroisoquinoline (3a): light yellow oil; 1H NMR (600 MHz, CDCl3) δ (ppm) 7.18 (m, 6H), 6.89 (d, J=8.2 Hz, 2H), 6.73 (t, J=7.1 Hz, 1H), 5.89–5.82 (m, 1H), 5.06 (t, J=13.1 Hz, 2H), 4.74 (t, J=6.7 Hz, 1H), 3.72–3.52 (m, 2H), 3.08–2.96 (m, 1H), 2.88 (dt, J=15.7, 5.2 Hz, 1H), 2.78–2.65 (m, 1H), 2.49 (dt, J=14.1, 7.2 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ (ppm) 149.4, 138.1, 135.6, 134.9, 129.2, 128.5, 127.3, 126.5, 125.7, 117.2, 117.0, 113.8, 59.3, 41.9, 40.9, 27.4; HRMS: m/z (ESI) calculated [M+H]+ 250.1590, measured 250.1594.

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Correspondence to Liangqiu Lu or Wen-Jing Xiao.

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Feng, Z., Zeng, T., Xuan, J. et al. C–H allylation of N-aryl-tetrahydroisoquinolines by merging photoredox catalysis with iodide catalysis. Sci. China Chem. 59, 171–174 (2016). https://doi.org/10.1007/s11426-015-5548-x

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  • DOI: https://doi.org/10.1007/s11426-015-5548-x

Keywords

  • visible light photocatalysis
  • iodide catalysis
  • allylation
  • tetrahydroisoquinolines