NHC-Catalyzed Annulation of Enals to 2,4-Dien-1-ones: Efficient Diastereoselective Synthesis of 1,3-Diaryl-4-styrenyl Cyclopentenes

Abstract

Nucleophilic heterocyclic carbene (NHC)-catalyzed ­annulation strategy has been utilized for the efficient synthesis of styrenyl-substituted cyclopentenes from 2,4-dienones.

Key words

NHC - catalysis - homoenolate - annulation - cyclopentene

• References and Notes

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• 18 Synthesis of (E)-1-Methoxy-4-(3-phenyl-5-styrylcyclopent-2-enyl)benzene (3a): 1,5-Diphenylpenta-2,4-dien-1-one (117 mg, 0.5 mmol), 4-methoxycinnamaldehyde (162 mg, 1 mmol) and IMesCl (15 mol%) were taken in a 25-mL round-bottom flask. Into this was added anhyd CH₂Cl₂ (5 mL) followed by DBU (20 mol%) and the reaction mixture was stirred under an inert atmosphere of argon. The completion of the reaction was monitored by TLC. After the completion of the reaction, the reaction mixture was subjected to column chromatography on 100–200 mesh silica gel using EtOAc–hexane (2:98) mixture, affording the styryl cyclopentene 3a (85%) as a colorless liquid. Chemical formula: C₂₆H₂₄O. ¹H NMR (500 MHz, CDCl₃): δ = 7.49 (d, J = 7.9 Hz, 2 H), 7.34 (t, J = 7.7 Hz, 4 H), 7.27 (dd, J = 13.0, 5.8 Hz, 3 H), 7.18 (t, J = 6.0 Hz, 1 H), 7.15 (d, J = 8.1 Hz, 2 H), 6.83 (d, J = 7.9 Hz, 2 H), 6.40 (dd, J = 15.8, 8.2 Hz, 1 H), 6.28 (d, J = 15.8 Hz, 1 H), 6.19 (s, 1 H), 3.85 (d, J = 7.8 Hz, 1 H), 3.79 (s, 3 H), 3.12 (dd, J = 15.2, 8.2 Hz, 1 H), 2.99 (p, J = 8.0 Hz, 1 H), 2.79 (dd, J = 15.2, 7.8 Hz, 1 H). ¹³C NMR (126 MHz, CDCl₃): δ = 158.3, 142.1, 137.5, 136.5, 136.1, 133.0, 129.8, 128.6, 128.5, 128.5, 128.4, 127.4, 127.0, 126.1, 125.7, 113.9, 57.8, 55.1, 53.2, 39.8.