Tunable Condensations between Ninhydrin and Sulfonium Salts Catalyzed by SeO₂ and Cs₂CO₃ Leading to Highly Functionalized Vinyl Alcohols or Vinyl Sulfides

Abstract

Condensation reactions between ninhydrin and sulfonium salts catalyzed by SeO₂ and Cs₂CO₃ afforded highly functionalized vinyl alcohols and vinyl sulfides. In the reaction of ninhydrin with dipropyl phenacylsulfonium bromide catalyzed by SeO₂ at room temperature in MeCN, highly functionalized vinyl alcohols were formed in good yields and high selectivities. When dimethyl phenacylsulfonium iodide was used in place of dipropyl phenacylsulfonium bromide, vinyl sulfides were produced in moderate to good yields.

catalysis - condensation - ninhydrin - selenium - sulfur ylide

References and Notes

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<A NAME="RW16808ST-10">10</A>

Typical Procedure for Preparing Compound 3
A mixture of ninhydrin (1, 178 mg, 1.0 mmol), dipropyl phenacylsulfonium bromide (2c, 317 mg, 1.0 mmol), SeO₂ (22 mg, 0.2 mmol), and Cs₂CO₃ (33 mg, 0.1 mmol) in MeCN (10 mL) was stirred for 7 h at r.t. After complete consumption of the starting materials (TLC), MeCN was removed in vacuum to give yellow solid. The residue was treated with aq H₂SO₄ (10%, 1 mL) followed by brine (10 mL), and extracted with CH₂Cl₂ (2 × 50 mL). The combined organic layers were dried over anhyd Na₂SO₄. The extracts were then concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: PE-EtOAc) on SiO₂ to give a 83% yield of 3a.
^¹H NMR (500 MHz, CDCl₃): δ = 8.07 (d, J = 7.4 Hz, 1 H), 7.98 (d, J = 7.5 Hz, 2 H), 7.91-7.84 (m, 3 H), 7.65 (t, J = 7.4 Hz, 1 H), 7.52 (t, J = 7.8 Hz, 2 H) ppm. ^¹³C NMR (125 MHz, CDCl₃): δ = 189.24, 186.09, 185.49, 142.78, 139.22, 138.95, 136.21, 136.20, 134.67, 132.37, 131.09, 129.48, 129.06, 124.03, 123.95 ppm. IR (KBr): ν = 1737, 1699, 1670, 1622, 1589, 1451, 1354, 1330, 1246, 1121, 1060, 810, 741, 688 cm^-¹. ESI-MS: m/z (%) = 277.2 (100) [M⁺ - H]. Anal. Calcd for C₁₇H₁₀O₄: C, 73.38; H, 3.62. Found: C, 73.33; H, 3.61.

<A NAME="RW16808ST-11">11</A>

Typical Procedure for Preparing Compound 4 A mixture of ninhydrin (1, 178 mg, 1.0 mmol), dimethyl phenacylsulfonium iodide (2d, 308 mg, 1.0 mmol), SeO₂ (11 mg, 0.1 mmol), and Cs₂CO₃ (33 mg, 0.1 mmol) in MeCN (10 mL) was stirred for 4 h at r.t. After complete consumption of starting materials (TLC), MeCN was removed in vacuum to give yellow solid. The residue was treated with brine (10 mL) and extracted with CH₂Cl₂ (2 × 50 mL). The combined organic layers were dried over anhyd Na₂SO₄. The extracts were then concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: PE-EtOAc) on SiO₂ to give a 77% yield of 4a.
^¹H NMR (500 MHz, CDCl₃): δ = 8.02 (d, J = 7.7 Hz, 2 H), 7.92 (d, J = 7.3 Hz, 1 H), 7.76-7.68 (m, 3 H), 7.64 (t, J = 7.2 Hz, 1 H), 7.51 (d, J = 7.6 Hz, 2 H), 2.28 (s, 3 H) ppm. ^¹³C NMR (125 MHz, CDCl₃): δ = 190.68, 189.56, 185.92, 165.82, 141.61, 139.97, 134.95, 134.91, 134.73, 129.27, 128.71, 124.25, 123.36, 122.80, 14.46 ppm. IR (KBr): ν = 1672, 1595, 1551, 1451, 1351, 1246, 1153, 1076, 1043, 836, 737, 690 cm^-¹. ESI-MS: m/z (%) = 309.4 (100) [M⁺ + H]. Anal. Calcd for C₁₈H₁₂O₃S: C, 70.11; H, 3.92. Found: C, 70.15; H, 3.98.