A Brønsted Acid Catalyzed Easy Access to Conjugated Diene-­Diones from Tertiary Propargyl Alcohols and 1,3-Dicarbonyl ­Compounds

Dedicated to Late Mr. Balaram Chatterjee

Abstract

A simple protocol catalyzed by a Brønsted acid, trifluoromethanesulfonic acid (CF₃SO₃H), to synthesize conjugated diene-diones from easily accessible tertiary propargyl alcohols and 1,3-dicarbonyl compounds is described. Reactions are performed in an air atmosphere by using undried solvents with water being the environmentally benign side product of the process. Preliminary synthetic applications of the conjugated diene-diones in the formation of conjugated dieneones and furans are also reported herein.

Key words

Brønsted acid - catalysis - propargyl alcohols - 1,3-dicarbonyl compounds - conjugated diene-diones

Publication History

Received: 30 May 2022

Accepted after revision: 07 July 2022

Article published online:
30 September 2022

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• 8 Typical procedure for the synthesis of 1,3-diphenyl-2-(1,3,3-triphenylallylidene)propane-1,3-dione (3a): CF₃SO₃H (10 mol%) was added to a solution of propargylic alcohol 1a (1.0 mmol) and 1,3-dicarbonyl compound 2a (1.1 mmol) in DCE solvent (1 mL). The reaction mixture was allowed to stir at room temperature (25 ℃) for the time specified in Table 2. After completion of the reaction as monitored by TLC, the solvent was evaporated under reduced pressure. The resulting crude product was then directly purified by column chromatography (silica gel 100-200, petroleum ether 60-80 °C/EtOAc) to afford 3a in 87% yield. ¹H NMR (400 MHz, CDCl₃, ppm): δ = 7.89-7.87 (m, 2 H), 7.63-7.61 (m, 2 H), 7.46-7.42 (m, 1 H), 7.36-7.32 (m, 2 H), 7.26-7.22 (m, 1 H), 7.16-7.05 (m, 10 H), 7.02-7.00 (m, 2 H), 6.94-6.88 (m, 3 H), 6.82-6.79 (m, 2 H), 6.48 (s, 1 H). ¹³C NMR (100 MHz, CDCl₃, ppm): δ = 196.10, 194.62, 149.25, 148.21, 142.25, 139.68, 139.06, 138.03, 137.94, 137.35, 133.07, 132.86, 130.21, 129.72, 129.61, 128.83, 128.72, 128.64, 128.37, 128.26, 128.16, 128.07, 128.05, 128.01, 127.97, 127.30. HRMS: m/z calcd for C₃₆H₂₆O₂ [M + H]⁺: 491.2010; found: 491.2012