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Synlett 2025; 36(11): 1565-1568
DOI: 10.1055/a-2554-2855
letter
Hydrogen Atom Transfer Reactions

Palladium/TBADT-Cocatalyzed Acyl C–H Alkenylation of Aldehydes with Alkenyl Triflates

Yi Fang
a   Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. of China
,
Pei Fan
b   School of Chemical and Materials Engineering, Anhui Province Key Laboratory of Low Temperature Co-fired Materials, Huainan Normal University, Huainan, Anhui, 232038, P. R. of China
,
Chuan Wang  ∗
a   Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. of China
› Author Affiliations
This work is supported by the National Natural Science Foundation of China (22071230, 22271267, 22471256).
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Abstract

By merging palladium and tetrabutylammonium decatungstate as a hydrogen-atom-transfer photocatalyst, we accomplished the acyl C–H alkenylation of aldehydes with alkenyl triflates, enabling the synthesis of a variety of multi-substituted cyclic alkenes under mild conditions.

Key words

α,β-unsaturated ketones - alkenylation - acylation - palladium - hydrogen-atom transfer

Supporting Information

    Supporting information for this article is available online at https://doi-org.accesdistant.sorbonne-universite.fr/10.1055/a-2554-2855.
  • Supporting Information


Publication History

Received: 13 February 2025

Accepted after revision: 10 March 2025

Accepted Manuscript online:
10 March 2025

Article published online:
14 April 2025

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  • 11 Ethyl 2-Butyrylcyclohex-1-ene-1-carboxylate (3aa); Typical Procedure: Pd(TFA)2 (3.3 mg, 0.01 mmol, 5 mol%), tri-o-tolylphosphane (L4; 6.1 mg, 0.02 mmol, 10 mol%), tetrabutylammonium decatungstate (TBADT; 33.2 mg, 0.01 mmol, 5 mol%), and K3PO4 (46.6 mg, 0.22 mmol, 1.1 equiv) were placed in a Schlenk tube equipped with a stir bar. After the Schlenk tube was evacuated and filled with nitrogen (three cycles), MeCN (1.0 mL), ethyl 2-{[(trifluoromethyl)sulfonyl]oxy}cyclohex-1-ene-1-carboxylate (1a; 0.2 mmol, 1.0 equiv), and butyraldehyde (2a; 43.2 mg, 0.6 mmol, 3.0 equiv) were added under a positive flow of nitrogen. The resultant mixture was stirred and irradiated using two 34 W 390 nm LED lamps (Kessil PR160-390, 5 cm away, with adequate fans to maintain the reaction at room temperature) for 18 h. After exposure to air for 15 min, the crude materials were purified through column chromatography on silica gel (petroleum ether/ethyl acetate = 20:1) to give the product 3aa (34.1 mg, 76% yield). 1H NMR (500 MHz, CDCl3): δ = 4.17 (q, J = 7.1 Hz, 2 H), 2.57–2.52 (m, 2 H), 2.41–2.05 (m, 4 H), 1.72–1.64 (m, 6 H), 1.26 (t, J = 7.1 Hz, 3 H), 0.96 (t, J = 7.4 Hz, 3 H). 13C NMR (126 MHz, CDCl3): δ = 208.6, 167.0, 150.9, 126.5, 60.9, 43.1, 27.7, 24.7, 21.5, 21.3, 16.9, 14.1, 13.8. HRMS (ESI): m/z calcd. for C13H20NaO3 +: 247.1305; found: 247.1311.