Nickel-Catalyzed Annulation of Aliphatic Amides with Alkynyl­silanes: An Expeditious Approach to Five-Membered Lactams

Abstract

An expeditious approach for the synthesis of diverse five-membered lactams through nickel-catalyzed annulation of the C(sp³)–H bonds of aliphatic amides with alkynylsilanes assisted by an 8-aminoquinolinyl directing group is reported, delivering the corresponding lactam derivatives in moderate to high yields. It is worth noting that alkynylsilanes are employed for the first time as coupling partners in the transition-metal-catalyzed functionalization of C(sp³)–H bonds of aliphatic amides. Equimolar amounts of alkynylsilanes and aliphatic amides are utilized, which greatly increases the efficiency of this protocol.

Key words

five-membered lactams - nickel-catalyzed - annulations - C(sp³)–H bonds - aliphatic amides - alkynylsilanes

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• 23 Lactams 3 and 4; General Procedure A 25 mL sealed tube was charged with 2,2-disubstituted N-(quinolin-8-yl)propionamide 1 (0.1 mmol), alkynylsilane 2 (0.1 mmol), Ni(acac)₂ (2.57 mg, 0.01 mmol), Na₂CO₃ (31.8 mg, 0.3 mmol), Ag₂CO₃ (82.8 mg, 0.3 mmol), TBAI (110.8 mg, 0.3 mmol) and PhCF₃ (1.5 mL). The vial was then evacuated, filled with N₂ and the reaction mixture stirred at 150 °C for 24 h. The mixture was then cooled to room temperature, diluted with EtOAc (2 mL), filtered through a Celite pad, and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel, eluting with EtOAc/PE (1:5 to 1:2, v/v), to afford the desired alkylated product 3 or 4. (E)-5-Benzylidene-3,3-dimethyl-1-(quinolin-8-yl)pyrrolidin-2-one (3a) Yield: 32.5 mg (99%); yellow solid; R_f  = 0.51 (hexane/EtOAc, 2:1). ¹H NMR (400 MHz, CDCl₃): δ = 8.87 (dd, J ₁ = 1.2 Hz, J ₂ = 3.2 Hz, 1 H), 8.20 (dd, J ₁ = 1.2 Hz, J ₂ = 6.8 Hz, 1 H), 7.92 (dd, J ₁ = 1.2 Hz, J ₂ = 6.4 Hz, 1 H), 7.63–7.69 (m, 2 H), 7.41 (dd, J ₁ = 3.2 Hz, J ₂ = 6.8 Hz, 1 H), 7.21–7.25 (m, 2 H), 7.06–7.10 (m, 3 H), 5.28 (s, 1 H), 3.25 (dd, J ₁ = 1.2 Hz, J ₂ = 14.4 Hz, 1 H), 3.13 (dd, J ₁ = 1.2 Hz, J ₂ = 14.4 Hz, 1 H), 1.53 (s, 3 H), 1.43 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 181.1, 151.1, 144.3, 143.0, 137.0, 136.1, 133.4, 130.4, 129.6, 129.3, 128.3, 127.6, 126.4, 125.2, 121.9, 104.4, 41.2, 40.9, 26.1, 25.7. HRMS (EI-TOF): m/z [M]⁺ calcd for C₂₂H₂₀N₂O: 328.1576; found: 328.1574.