Temperature-Controlled Selectivity toward [1,3]- or [3,3]-Sigmatropic Rearrangement: Regioselective Synthesis of Substituted 3,4-Dihydrocoumarins

Abstract

Either [1,3]- or [3,3]-sigmatropic rearrangements were selectively accessed by controlling the reaction temperature in the gold(III)-catalyzed tandem rearrangement/cyclization of (E)-2-(aryloxymethyl)alk-2-enoates to afford diversely substituted 3,4-dihydrocoumarin derivatives in moderate to good yields and in excellent regioselectivity.

Key words

[1,3]-sigmatropic rearrangement - [3,3]-sigmatropic rearrangement - gold catalyst - tandem reaction - 3,4-dihydrocoumarin

References and Notes

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15

Typical Experimental Procedure for the Synthesis of 2 under Condition A: AuCl₃ (9.1 mg, 0.03 mmol), AgOTf (23.1 mg, 0.09 mmol), and DCE (2 mL) were added to a 10-mL flask. The mixture was stirred at r.t. for 5 min before a DCE solution of 1a (0.35 g, 1.0 mmol diluted in 1 mL of solvent) was added. Then the reaction mixture was stirred at 80 ˚C for 4 h. Upon completion of the reaction, the resulting mixture was diluted with CH₂Cl₂ (10 mL) and filtered through Celite. After evaporation of the solvent under vacuum, the residue was purified by column chromatog-raphy on silica gel (200-300 mesh) using cyclohexane-EtOAc (12:1) as eluent to give pure 2a.
Typical Experimental Procedure for the Synthesis of 3 under Condition B: AuCl₃ (9.1 mg, 0.03 mmol), AgOTf (23.1 mg, 0.09 mmol), and DCE or DCB (2 mL) were added to a 10-mL sealed vessel. The mixture was stirred at r.t. for 5 min before a DCE or DCB solution of 1a (0.35 g, 1.0 mmol diluted in 1 mL of solvent) was added. Then the reaction mixture was stirred at 120 ˚C for 2 h. Upon completion of the reaction, the resulting mixture was diluted with CH₂Cl₂ (10 mL) and filtered through Celite. After evaporation of the solvent under vacuum, the residue was purified by column chromatography on silica gel (200-300 mesh) using cyclohexane-EtOAc (12:1) as eluent to give pure 3a.

16

Representative Data for Compound 2 and 3:
Compound 2b: white solid; R _f 0.46 (cyclohexane-EtOAc, 12:1); mp 198.3-201.0 ˚C. ^¹H NMR (500 MHz, CDCl₃): δ = 4.32 (d, 2 H, J = 2.5 Hz, CH₂), 7.25 (d, 1 H, J = 8.5 Hz, ArH), 7.43-7.85 (m, 9 H, ArH), 8.03 (t, 1 H, J = 2.5 Hz, ArCH=). ^¹³C NMR (125 MHz, CDCl₃): δ = 26.12, 112.14, 117.50, 122.28, 122.91, 124.27, 125.25, 127.33, 128.87, 129.25, 130.76, 130.91, 131.74, 132.17, 133.55, 142.13, 147.77, 163.60. IR (KBr): 1711 (C=O), 1630 (C=C) cm^-¹. GC-MS: m/z = 364 [M⁺], 366 [M⁺ + 2]. HRMS (EI): m/z calcd for C₂₀H₁₃O₂Br: 364.0099; found: 364.0113.
Compound 3c: white solid; R _f 0.56 (cyclohexane-EtOAc, 12:1); mp 114.5-114.6 ˚C. ^¹H NMR (500 MHz, CDCl₃): δ = 2.28 (s, 3 H, Me), 4.90 (s, 1 H), 5.72 (s, 1 H), 6.44 (s, 1 H), 6.89-7.33 (m, 8 H, ArH). ^¹³C NMR (125 MHz, CDCl₃): δ = 20.80, 48.26, 117.04, 124.28, 127.52, 127.76, 128.96, 129.08, 129.26, 129.43, 134.53, 136.88, 140.77, 148.59, 163.26. IR (KBr): 1746 (C=O), 1627 (C=C) cm^-¹. GC-MS: m/z = 250 [M⁺]. HRMS (EI): m/z calcd for C₁₇H₁₄O₂: 250.0994; found: 250.1001.