A Convenient Solid-Phase Synthesis of Coumarins by TMSOTf-Catalyzed Intramolecular Seleno-Arylation of Tethered Alkenes

Abstract

TMSOTf-catalyzed intramolecular seleno-arylation of tethered alkenes was performed using polystyrene-supported succinimidyl selenide as the selenium source. This catalytic process provides an efficient method for the regioselective synthesis of dihydrocoumarins possessing a seleno functionality, followed by syn elimination of selenoxides to provide coumarins in good yields and purities. Suzuki cross-coupling reaction of the resin-bound bromodihydrocoumarin was also performed, and biphenyl coumarin was obtained by subsequent cleavage of selenium linker.

selenium - cyclization - TMSOTf - coumarins - solid-phase synthesis - carbon-carbon bond formation - catalysis

References and Notes

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<A NAME="RW76411ST-27">27</A>

Typical Procedure for the Preparation of Polystyrene-Supported Allyl Selenide (2)
To a suspension of the swollen polystyrene-supported selenenyl bromide (1, Br: 0.99 mmol/g, 2.5 g) in dry THF-DMF (v/v = 5:1, 30 mL) was added NaBH₄ (5 mmol) under nitrogen atmosphere at 40 ˚C. After stirring for 8 h at 40 ˚C, 3-bromoprop-1-ene (5.5 mmol) was added dropwise under nitrogen atmosphere, and stirred for another 12 h. The resin 2 was collected by filtration, washed with THF (2 × 20 mL), MeOH (2 × 20 mL), and CH₂Cl₂ (2 × 20 mL), and dried in vacuum.

<A NAME="RW76411ST-28">28</A>

Typical Procedure for the Preparation of 6-Methyl-4-phenyl-3-(phenylselenyl)-2 H -chromen-2-one [(±)-6]
To an oven-dried flask (25 mL) was added polystyrene-supported succinimidyl selenide (PSSS, 0.27 g, 1.05 mmol) in dry CH₂Cl₂ (10 mL) under nitrogen atmosphere, and the solution was cooled at -78 ˚C. Trimethylsilyl trifluoro-methanesulfonate (TMSOTf, 0.022 g, 0.1 mmol) was added. After stirring for 0.5 h at -78 ˚C, p-tolyl cinnamate (0.238 g, 1.0 mmol) was added under nitrogen atmosphere. The mixture was stirred for another 2 h at -78 ˚C and then stored in a freezer at -20 ˚C for 8 h. Saturated aq NaHCO₃ (5 mL) was poured into the flask to quench reaction mixture. The organic phase was separated, and the aqueous phase was extracted with fresh portion of CH₂Cl₂ (25 mL). The extracts were combined, washed with H₂O, and dried over MgSO₄. After filtering and concentrating under reduced pressure by rotary evaporation at r.t, the oily residue was subjected to preparative TLC on silica gel with EtOAc-light PE (1:9) as eluent to give 197 mg of (±)-6 (50% isolated yield).

<A NAME="RW76411ST-29">29</A>

General Procedure for the Preparation of 2 H -Chromen-2-one (5)
To a suspension of the swollen resin 2 (1.0 g) in dry CH₂Cl₂ (15 mL) was added NCS (0.668 g, 5.0 mmol) at 0 ˚C. The mixture was stirred for 0.5 h at 0 ˚C and 2 h at r.t. After filtrating and washing with dry CH₂Cl₂ (3 × 15 mL), PSSS was suspended with dry CH₂Cl₂ (15 mL) and cooled to -78 ˚C. TMSOTf (0.022 g, 0.10 mmol) was added. After stirring for 0.5 h at -78 ˚C, substituted phenyl acrylate 3 (5.0 mmol) was added under nitrogen atmosphere. The suspension was stirred for another 2 h at -78 ˚C and then stored in a freezer at -20 ˚C for 8 h. Saturated aq NaHCO₃ (5 mL) was poured into the flask to quench the reaction mixture. 3-Polystyrene-supported seleno-3,4-2H-chromen-2-one [(±)-4] was collected by filtration, washed with THF (2 × 20 mL), Et₂O (2 × 20 mL), THF-H₂O (3:1, 2 × 20 mL), H₂O (2 × 20 mL), THF (2 × 20 mL), benzene (2 × 20 mL), MeOH (2 × 20 mL), and CH₂Cl₂ (2 × 20 mL), and dried under vacuum. The washed resin (±)-4 was suspended in THF (15 mL). To the mixture was added 30% aq H₂O₂ (1.2 mL). The mixture was stirred for 1 h at 0 ˚C and then for another 20 min at r.t. The mixture was filtered, and the resin was washed with CH₂Cl₂ (2 × 15 mL). The filtrate was washed with H₂O (2 × 30 mL), dried over MgSO₄, and evaporated to dryness in vacuum to afford 2H-chromen-2-ones 5.

<A NAME="RW76411ST-30">30</A>

Typical Procedure for the Preparation of 4-Biphenyl-2 H -chromen-2-one (10)
To a suspension of the swollen resin (±)-4d (0.5 g) in dry THF (15 mL) was added Pd(OAc)₂ (0.0056 g, 0.025 mmol), phenylboronic acid (0.61 g, 5.0 mmol), KF (0.58 g, 10.0 mmol), and 2-(dicyclohexylphosphino)biphenyl [o-(biphenyl)PCy₂] (0.175 g, 0.5 mmol) under a nitrogen atmosphere. The reaction mixture was stirred at r.t. for 24 h. Resin (±)-9 was collected by filtration, washed with THF (2 × 20 mL), Et₂O (2 × 20 mL), THF-H₂O (3:1, 2 × 20 mL), H₂O (2 × 20 mL), THF (2 × 20 mL), benzene (2 × 20 mL), MeOH (2 × 20 mL), and CH₂Cl₂ (2 × 20 mL), and dried in vacuum. The washed resin (±)-9 was suspended in THF (15 mL). To the mixture was added 30% aq H₂O₂ (1.5 mL) and stirred for 1.5 h at 0 ˚C, and stirred for another 20 min at r.t. The mixture was filtered, and the resin was washed with CH₂Cl₂ (2 × 15 mL). The filtrate was washed with H₂O (2 × 30 mL), dried over MgSO₄, and evaporated to dryness under vacuum to afford 4-biphenyl-2H-chromen-2-one (10).

<A NAME="RW76411ST-31">31</A>

6-Methyl-4-phenyl-3-(phenylselenyl)-2 H -chromen-2-one [(±)-6]
Yellow oil. ^¹H NMR (400 MHz, CDCl₃): δ = 7.35-7.07 (11 H, m), 6.86 (2 H, dt, J ₁ = 8.4 Hz, J ₂ = 2.8 Hz), 4.58 (1 H, d, J = 10.8 Hz), 4.04 (1 H, d, J = 10.4 Hz), 2.33 (3 H, s). ^¹³C NMR (100 MHz, CDCl₃): δ = 170.10, 148.59, 135.90, 135.65, 135.47, 129.97, 129.07, 128.96, 128.78, 128.54, 128.44, 127.79, 121.12, 79.10, 51.07, 20.96. IR (KBr): ν = 1741, 1496, 1431, 1208, 1010, 736, 693 cm^-¹. HRMS:
m/z [M]⁺ calcd for C₂₂H₁₈O₂Se: 394.0472; found: 394.0470.