One-Pot Synthesis of 1,2-Dihydronaphthalenes by Cu-Catalyzed Reaction of 2-(Alkynyl)benzaldehydes and Alcohols

Abstract

The reaction of 2-(alkynyl)benzaldehydes with alcohols in the presence of copper catalyst resulted in the selective synthesis of the 1,2-dihydronaphthalene derivatives. On the reaction, it was proposed that the reaction proceeds via the intramolecular dehydration of alcohols followed by the reaction with 2-(alkynyl)benzaldehydes.

Key words

2-(alkynyl)benzaldehyde - alcohol - 1,2-dihydronaphthalene - dehydration - cyclization - copper catalyst

Publication History

Received: 29 September 2022

Accepted after revision: 12 October 2022

Accepted Manuscript online:
12 October 2022

Article published online:
28 November 2022

• References and Notes

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• 10 General Procedure A solution of the corresponding alcohol (0.50 mmol), 2-(alkynyl)benzaldehyde (0.75 mmol), Cu(OTf)₂ (0.025 mmol, 9.0 mg) in ClCH₂CH₂Cl (3 mL) was heated at 80 ℃ for 8 h under a nitrogen atmosphere in a sealed tube. The reaction mixture was diluted with CHCl₃ and washed with saturated NaHCO₃ aq. and brine. The organic layer was dried over MgSO₄. After the removal of the solvent under reduced pressure, the residue was purified by chromatography on SiO₂. Further purification was carried out by recyclable preparative HPLC, if necessary. Representative Example 1-Benzoyl-1,2-dihydro-2,2-dimethylnaphthalene (2) ¹H NMR(400 MHz, CDCl₃): δ = 8.01 (d, J = 7.2 Hz, 2 H), 7.57 (t, J = 7.2 Hz, 1 H), 7.48 (dd, J = 7.6, 7.6 Hz, 2 H), 7.16 (ddd, J = 7.2, 7.2, 1.2 Hz, 1 H), 7.10 (dd, J = 7.2, 1.2 Hz, 1 H), 7.03 (ddd, J = 7.2, 7.2, 1.2 Hz, 1 H), 6.92 (d, J = 7.6 Hz, 1 H), 6.42 (d, J = 9.2 Hz, 1 H), 5.73 (d, J = 9.2 Hz, 1 H), 4.71 (s, 1 H), 1.17 (s, 3 H), 1.13 (s, 3 H).¹³C-NMR(400 MHz, CDCl₃): δ = 200.41, 138.67, 138.15, 133.43, 132.94, 132.91, 128.65, 128.47, 128.17, 127.40, 127.08, 126.64, 125.02, 54.87, 36.00, 28.54, 24.38. FT-IR (KBr): 3103, 3067, 3016, 2971, 2925, 1673, 1593, 1486, 1445, 1336, 1295, 1264, 1206, 989, 879, 842, 779, 741 cm^–1. MS (APCI): m/z = 262 [M⁺]. HRMS (APCI): m/z calcd for C₁₉H₁₈O: 262.1358; found: 262.1362.
• 11 Compound 7 was obtained as a single diastereomer determined by ¹H NMR spectroscopy. In the previous report (ref. 6a) by Asao and Yamamoto, the isomerization of cis isomer of this type dihydronaphthalene to the thermodynamically stable trans isomer occurred in the presence of Cu(OTf)₂. Therefore, we determined that 7 is the trans isomer.