Copper-Catalyzed γ-Cyanation of Aza-Baylis–Hillman Adducts Using Trimethylsilyl Cyanide

Arvind K. Yadav; Lal Dhar S. Yadav

doi:10.1055/s-0034-1380411

Synlett, Table of Contents

Synlett 2015; 26(08): 1026-1030
DOI: 10.1055/s-0034-1380411

letter

Copper-Catalyzed γ-Cyanation of Aza-Baylis–Hillman Adducts Using Trimethylsilyl Cyanide

Arvind K. Yadav

Green Synthesis Lab, Department of Chemistry, University of Allahabad, Allahabad 211002, India Email: ldsyadav@hotmail.com

,

Lal Dhar S. Yadav*

Green Synthesis Lab, Department of Chemistry, University of Allahabad, Allahabad 211002, India Email: ldsyadav@hotmail.com

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Abstract

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Abstract

A copper-catalyzed γ-cyanation of aza-Baylis–Hillman adducts via iminium ion formation adjacent to benzylic tertiary amines has been developed using tert-butyl hydroperoxide (TBHP) as the external oxidant. The protocol involves in situ formation of 4π-conjugated iminium ion intermediates that undergo nucleophilic attack by cyanide to provide valuable γ-cyanated α,β-unsaturated amines.

Key words

benzylic amines - Baylis–Hillman adducts - copper catalysis - cyanides - electron transfer - Michael addition

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References

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11 General Procedure for the Copper-Catalyzed γ-Cyanation of Aza-Baylis–Hillman Adducts (Table 3) A round-bottom flask was charged with aza-Baylis–Hillman adduct 1 (1.0 mmol), MeCN (3 mL), CuI (10 mol%), TBHP (2.0 equiv), and TMSCN (1.5 equiv). The flask was stoppered, and the reaction mixture was stirred at r.t. for 6–12 h (Table 3). After completion of the reaction (as monitored by TLC), H₂O (5 mL) was added, and the mixture was extracted with EtOAc (3 × 5 mL). The combined organic phases were dried over MgSO₄, filtered, and evaporated under reduced pressure. The resulting product was purified by silica gel column chromatography using a gradient mixture of hexane–EtOAc as eluent to afford an analytically pure sample of 2. All the compounds were characterized by NMR, IR, and MS analysis. The characterization data of representative compounds 2a, 2h, and 2k are given below. Compound 2a: yellow oily liquid. IR (neat liquid): ν_max = 3053, 3021, 2235, 2950, 2925, 2850, 2710, 1962, 1727, 1624, 1575, 1492, 1435, 1378, 1260, 1013, 767, 705 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.34–7.26 (m, 5 H), 3.76 (s, 3 H), 3.07 (s, 2 H), 2.35–2.33 (m, 4 H), 1.36–1.34 (m, 4 H). ¹³C NMR (100 MHz, CDCl₃): δ = 166.1, 156.2, 133.4, 128.3, 127.1, 126.9, 116.2, 95.9, 54.1, 52.3, 26.5, 13.1. HRMS (EI): m/z calcd for C₁₆H₁₈N₂O₂: 270.1368; found: 270.1365. Compound 2h: yellow oily liquid. IR (neat liquid): ν_max = 3023, 3067, 3023, 2957, 2923, 2858, 2713, 2232, 1693, 1632, 1572, 1497, 1437, 1379, 1264, 1197, 1148, 1013, 753, 715 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 9.56 (s, 1 H), 7.27–7.14 (m, 4 H), 7.08–6.76 (m, 5 H), 3.17 (t, J = 6.4 Hz, 2 H), 3.08 (t, J = 6.4 Hz, 2 H), 3.05 (s, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 187.7, 168.4, 144.1, 138.0, 134.3, 129.1, 127.6, 127.0, 125.3, 120.7, 118.8, 116.3, 109.2, 74.5, 51.7, 27.6, 12.3. HRMS (EI): m/z calcd for C₁₉H₁₆N₂O: 288.1263; found: 288.1261. Compound 2k: yellow oily liquid. IR (neat liquid): ν_max = 3107, 3064, 3020, 2963, 2920, 2854, 2713, 2237, 1722, 1621, 1572, 1495, 1434, 1370, 1263, 1197, 1148, 1012, 762, 711 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.32–7.24 (m, 4 H), 7.12–6.69 (m, 5 H), 3.66 (s, 3 H), 3.19 (t, J = 6.4 Hz, 2 H), 3.03 (t, J = 6.4 Hz, 2 H), 2.93 (s, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 168.5, 144.3, 137.6, 133.7, 126.2, 125.0, 124.7, 120.3, 118.3, 117.5, 115.2, 72.5, 52.3, 50.3, 42.7, 27.1, 24.5, 12.9. HRMS (EI): m/z calcd for C₂₀H₁₈N₂O₂: 318.1368; found: 318.1370.

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