Trimethylsilyl Triflate as an Efficient Catalyst for Intramolecular and Intermolecular Carbonyl–Alkyne Metathesis Reactions

Abstract

Trimethylsilyl triflate has emerged as a powerful and versatile Lewis acid catalyst in organic synthesis, offering high efficiency under mild reaction conditions. It is known for its strong electrophilic activation and is widely used for C–C bond formation, heterocyclic synthesis, and protecting-group transformations. Herein, a straightforward synthesis of various biologically and synthetically important compounds, including 2H-chromenes, coumarins, furans, pyrans, and chalcones, has been achieved through carbonyl–alkyne metathesis reactions with trimethylsilyl triflate as a Lewis acid catalyst.

Key words

carbonyl–alkyne metathesis - chromenes - coumarins - chalcones - trimethylsilyl triflate - organocatalysis

Publikationsverlauf

Eingereicht: 29. Januar 2025

Angenommen nach Revision: 21. März 2025

Accepted Manuscript online:
21. März 2025

Artikel online veröffentlicht:
01. Juli 2025

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• 11 2H-Chromenes 2a–j; General Procedure TMSOTf (20 mol%) was added to a stirred solution of the appropriate 2-(propargyloxy)benzaldehyde 1 (1 equiv) in DCE (10 mL) and the mixture mixture was heated at 80 °C for 4–10 h until the reaction was complete. H₂O (20 mL) was then added and the mixture was extracted with Et₂O (3 × 20 mL). The combined organic extracts were washed with brine, dried (Na₂SO₄), and concentrated under reduced pressure. The crude product was purified by column chromatography. 2H-Chromen-3-yl(phenyl)methanone (2a) Prepared according to the general procedure from 1a (120 mg, 0.5 mmol) as a yellowish oil; yield: 113 mg (94%). IR (ATR): 3058, 2921, 2854, 1621, 1454, 1334, 1224, 1137, 1012, 923, 757 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.72 (dd, J = 5.1, 3.3 Hz, 2 H), 7.58 (ddd, J = 6.7, 3.9, 1.3 Hz, 1 H), 7.49 (dd, J = 10.4, 4.6 Hz, 2 H), 7.29 (dd, J = 7.8, 1.4 Hz, 1 H), 7.14–7.08 (m, 2 H), 6.96–6.88 (m, 2 H), 5.17 (d, J = 1.1 Hz, 2 H). 13C NMR (101 MHz, CDCl₃): δ = 194.1, 155.6, 137.6, 137.1, 132.6, 132.0, 129.8, 129.4, 129.0, 128.5, 121.9, 121.0, 116.4, 65.3. The spectroscopic data matched those previously reported.^6f