N,N,N-Triphenylselenylisocyanuric Acid (TPSCA): A New Versatile Reagent for α-Phenylselenenylation of Aldehydes and Ketones

Abstract

A new, versatile reagent, N,N,N-triphenylselenyl-isocyanuric acid (TPSCA) has been prepared, characterized, and used as a source of the electrophilic phenylselenyl group. This relatively stable compound was utilized for an efficient α-selenenylation reaction of aldehydes and ketones catalyzed by l-prolinamide under mild reaction conditions. The organocatalytic asymmetric α-selenenylation of an aldehyde was also studied and the reaction was found to proceed with high enantioselectivity (96% ee).

Key words

electrophilic selenenylation - isocyanuric acid - aldehydes - ketones - prolinamide

• References and Notes

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• 19 Preparation of N,N,N-(Triphenylselenyl)isocyanuric Acid (TPSCA, 3): Cyanuric acid (1; 0.129 g, 1 mmol) was added to a solution of KOH (0.168 g, 3 mmol) in H₂O (10 mL). The mixture was heated to 90 °C for 30 min, and then cooled to room temperature. A solution of silver nitrate (0.850 g, 5 mmol) in H₂O (10 mL) was added dropwise, with stirring, to the above mixture. After 1 h, the white precipitate was collected by filtration, washed with water, and dried at 105 °C to give the silver salt of isocyanuric acid 2 (0.337 g, 75%) as a white solid. The anhydrous silver salt 2 (0.90 g, 2 mmol) was added to a solution of phenylselenyl bromide²⁴ (1.652 g, 7 mmol) in anhydrous CH₂Cl₂ (10 mL), and the mixture was stirred at room temperature under an argon atmosphere. After 2 h, precipitated AgBr was filtered off and the filtrate was evaporated under reduced pressure; anhydrous n-hexane (10 mL) was added, and the crude solid product was collected and subjected to preparative TLC (silica gel; n-hexane–EtOAc, 4:1) to afford TPSCA 3 (0.89 g, 75%) as a white solid; mp 143–145 °C. IR (KBr): 1703 cm^–1. ¹H NMR (300 MHz, DMSO-d₆): δ = 7.82 (s, 6 H), 7.57 (s, 9 H). ¹³C NMR (75 MHz, DMSO-d₆): δ = 148.9, 131.7, 129.1, 125.9. MS: m/z = 597 [⁸⁰Se₃]. Anal. Calcd for C₂₁H₁₅N₃O₃Se₃: C, 42.21; H, 2.51; N, 7.03. Found: C, 41.97; H, 2.81; N, 6.13.
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• 22 General Procedure for α-Selenenylation of Aldehydes and Ketones: To a solution of aldehyde or ketone (3 mmol) and l-prolinamide (5 mol%) in anhydrous CH₂Cl₂ (6 mL), was added TPSCA 3 (1 mmol) at room temperature. The mixture was stirred in the presence of 4Ǻ molecule sieves under an argon atmosphere for the appropriate time (Table 2). When the reaction was complete (TLC), the reaction mixture was treated with water (5 mL) and the solution was extracted with ethyl acetate (3 × 15 mL). The combined extracts were dried over MgSO₄, filtered, and concentrated in vacuo. The resulting residue was further purified by preparative TLC (silica gel; n-hexane). The identity and purity of the products were confirmed by IR, ¹H NMR, and ¹³C NMR spectroscopic analysis. 2-(Phenylseleno)heptanal (5b) Yield: 0.59 g (78%); pale-yellow oil. IR (neat): 1709 cm^–1. ¹H NMR (300 MHz, CDCl₃): δ = 9.39 (d, J = 3.7 Hz, 1 H), 7.58–7.49 (m, 2 H), 7.34–7.25 (m, 3 H), 3.63–3.57 (m, 1 H), 1.72–1.43 (m, 4 H), 1.33–1.28 (m, 4 H), 0.89 (t, J = 6.6 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 193.3, 136.0, 129.33, 129.32, 126.4, 53.2, 31.6, 28.1, 28.0, 22.9, 14.3. 3-Phenyl-2-(phenylseleno)propionaldehyde (5d) Yield: 0.73 g (84%); pale-yellow oil. IR (neat): 1688 cm^–1. ¹H NMR (300 MHz, CDCl₃): δ = 9.48 (d, J = 4.0 Hz, 1 H), 7.39 (d, J = 7.5 Hz, 2 H), 7.25–6.95 (m, 6 H), 6.86–6.75 (m, 2 H), 3.95–3.84 (m, 1 H), 3.36 (dd, J = 10.9, 8.0 Hz, 1 H), 3.03 (dd, J = 10.9, 6.0 Hz, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 194.6, 138.0, 134.5, 131.5, 129.4, 129.0, 128.9, 126.3, 45.3, 28.1. 2-(Phenylselenyl)cyclopentanone (5i) Yield: 0.55 g (75%); pale-yellow oil. IR (neat): 1730 cm^–1. ¹H NMR (300 MHz, CDCl₃): δ = 7.94 (dd, J = 6.5, 1.5 Hz, 2 H), 7.62–7.44 (m, 3 H), 3.77–3.74 (m, 1 H), 2.32–2.27 (m, 2 H), 2.04–1.92 (m, 4 H). ¹³C NMR (75 MHz, CDCl₃): δ = 211.0, 134.4, 128.6, 128.0, 127.4, 45.7, 35.6, 29.6, 20.0. 1-Methyl-3-(phenylselenyl)piperidin-4-one (5k) Yield: 0.65 g (80%); pale-orange oil. IR (neat): 1709 cm^–1. ¹H NMR (300 MHz, CDCl₃): δ = 7.60–7.55 (m, 2 H), 7.33–7.16 (m, 3 H), 3.80 (br s, 1 H), 3.36–3.30 (m, 1 H), 3.21–3.17 (m, 1 H), 2.90–2.80 (m, 2 H), 2.49–2.46 (m, 1 H), 2.24 (s, 3 H), 2.19–2.15 (m, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 205.58, 134.4, 129.9, 129.7, 128.6, 61.5, 55.6, 50.2, 45.8, 37.1. 2-(Phenylselenyl)pentan-3-one (5l) Yield: 0.53 g (73%); pale-yellow oil. IR (neat): 1702 cm^–1. ¹H NMR (300 MHz, CDCl₃): δ = 7.53–7.50 (m, 2 H), 7.35–7.26 (m, 3 H), 3.82 (q, J = 7.0 Hz, 1 H), 2.80 (dq, J = 17.3, 7.3 Hz, 1 H), 2.50 (dq, J = 17.3, 7.3 Hz, 1 H), 1.49 (d, J = 7.0, 3 H), 1.08 (t, J = 7.3 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 207.6, 135.8, 128.9, 128.7, 127.1, 45.0, 33.0, 16.5, 8.4. 1-Phenyl-2-(phenylselanyl)propanone (5m) Yield: 0.62 g (72%); pale-orange oil. IR (neat): 1673 cm^–1. ¹H NMR (300 MHz, CDCl₃): δ = 7.87 (d, J = 8.7 Hz, 2 H), 7.54–7.40 (m, 6 H), 7.29–7.26 (m, 2 H), 4.70 (q, J = 6.8 Hz, 1 H), 1.65 (d, J = 6.8 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 196.3, 137.0, 136.6, 133.0, 132.8, 129.0, 129.3, 129.0, 128.9, 128.7, 39.7, 17.6.
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