Nickel-Catalyzed Decarbonylative Alkynylation of Acyl Fluorides with Terminal Alkynes under Copper-Free Conditions

Abstract

Nickel-catalyzed decarbonylative alkynylation of acyl fluorides with terminal silylethynes under copper-free conditions is described. This newly developed method has a wide substrate scope, affording internal silylethynes in moderate to high yields. The formation of 1,3-diynes as homocoupled products and conjugate enones as carbonyl-retentive products were effectively suppressed.

Key words

nickel catalysis - decarbonylation - silylalkynes - alkynylation - acyl fluorides - sila-Sonogashira–Hagihara reaction

Publication History

Received: 09 September 2020

Accepted after revision: 21 September 2020

Article published online:
28 October 2020

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• 28 Silylated Internal Alkynes 3: General Procedure An oven-dried 20 mL Schlenk tube containing a magnetic stirring bar was charged with Ni(cod)₂ (5.5 mg, 0.02 mmol, 10 mol%), DPPP (12.4 mg, 0.03 mmol, 15 mol%), 1,4-dioxane (1 mL) under dry N₂, and the mixture was stirred for 30 s at r.t. The appropriate acyl fluoride 1 (0.2 mmol), silyl alkyne 2 (0.4 mmol), and Bu₃N (0.3 mmol) were added, and the mixture was heated at 140 °C in a heating block with stirring for 24 h, then cooled to r.t. The reaction was quenched with sat. aq NH₄Cl, and the mixture was extracted with Et₂O. The combined organic phase was dried (MgSO₄) and concentrated under vacuum, and the residue was purified by column chromatography (silica gel, EtOAc–hexane). Triisopropyl(2-naphthylethynyl)silane (3aa)¹³ Yellow oil; yield: 53.6 mg (87%); R_f = 0.54 (hexane). ¹H NMR (400 MHz, CDCl₃): δ = 1.19 (s, 21 H), 7.48–7.50 (m, 2 H), 7.54 (dd, J = 8.4, 2.0 Hz, 1 H), 7.76–7.82 (m, 3 H), 8.02 (s, 1 H). ¹³C{¹H} NMR (101 MHz, CDCl₃): δ = 11.5, 18.9, 91.1, 107.6, 121.0, 126.6, 126.8, 127.85, 127.87, 128.0, 129.0, 132.0, 133.0, 133.1.