Rapid Access to Functionalized γ-Lactams through Copper-Catalyzed Oxidative Cyclization of Diynes

Abstract

An efficient copper-catalyzed oxidative cyclization of diynes is described. A range of functionalized γ-lactams can be readily constructed by using this protocol. This copper-catalyzed oxidative process proceeds through an alkyne oxidation, carbene/alkyne metathesis, and donor–donor carbene oxidation sequence. The use of readily available substrates, high flexibility, a simple procedure, and mild reaction conditions render the procedure a viable alternative for the preparation of functionalized γ-lactams.

Key words

copper catalysis - diynes - oxidation - carbene/alkyne metathesis - γ-lactams

Publication History

Received: 13 September 2022

Accepted after revision: 07 October 2022

Accepted Manuscript online:
07 October 2022

Article published online:
21 November 2022

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• 17 4-Benzoyl-3-phenyl-1-tosyl-1,5-dihydro-2H-pyrrol-2-one (3a); Typical Procedure A mixture of sulfonamide 1a (0.2 mmol, 77.0 mg), 3,5-dichloropyridine N-oxide (2a, 0.6 mmol, 98.4 mg), and Cu(MeCN)₄PF₆ (0.02 mmol, 7.5 mg) in DCE (4.0 mL) was heated at 80 °C (heating mantle temperature) until the reaction was complete (TLC; typically 2 h). The mixture was then concentrated, and the residue was purified by chromatography [silica gel, PE–EtOAc (5:1)] to give a pale-yellow oil; yield: 71.2 mg (85%). IR (neat): 2923, 1724, 1653, 1596, 1493, 1448, 1365, 1328, 1254, 1188, 1172, 1115, 1090, 963, 667 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 8.04 (d, J = 7.6 Hz, 2 H), 7.67 (d, J = 7.3 Hz, 2 H), 7.46 (t, J = 6.8 Hz, 1 H), 7.37 (d, J = 7.6 Hz, 2 H), 7.29–7.26 (m, 4 H), 7.21–7.13 (m, 3 H), 4.80 (s, 2 H), 2.44 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 192.5, 166.6, 147.6, 145.6, 136.4, 134.8, 134.4, 134.2, 129.9, 129.7, 129.4, 129.2, 128.7, 128.6, 128.4, 128.3, 50.6, 21.7. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₄H₂₀NO₄S: 418.1108; found: 418.1106.