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Synlett 2015; 26(08): 1026-1030
DOI: 10.1055/s-0034-1380411
DOI: 10.1055/s-0034-1380411
letter
Copper-Catalyzed γ-Cyanation of Aza-Baylis–Hillman Adducts Using Trimethylsilyl Cyanide
Further Information
Publication History
Received: 04 January 2015
Accepted after revision: 16 February 2015
Publication Date:
16 March 2015 (online)
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.
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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): νmax = 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): νmax = 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): νmax = 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.
For recent articles, see:
For selected examples, see:
For selected articles on Baylis–Hillman reaction, see:
For recent developments in nitrogen radical cation chemistry, see:
For selected articles on electrochemical cyanation of amines, see: