Nucleophilic Ring Opening of Mono-Activated Cyclopropanes with Aryl­selenolates Generated from Diselenides in the Presence of a Zn/AlCl₃ System

Abstract

An efficient one-pot synthesis of γ-arylselenenyl ketones, acids, and nitriles is presented. The method uses Zn/AlCl₃-promoted cleavage of diselenides and subsequent ring-opening of mono-activated cyclopropanes.

Key words

mono-activated cyclopropanes - ring opening - disele­nides - zinc selenolates - zinc

References and Notes

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12

General Procedure: A mixture of diaryl diselenide (0.5 mmol) and zinc powder (3.0 mmol) in anhydrous MeCN (15 mL), was stirred at 70 ˚C. After 15 min, anhydrous AlCl₃ (3.0 mmol in 2 mL anhydrous MeCN) was added cautiously. The mixture was stirred for 1 h at 70 ˚C, until the yellow solution turned colorless. The mono-activated cyclopropane (1.1 mmol) was then added to the solution and the mixture was stirred at 70 ˚C for the period of time specified in Table  [¹] . The progress of reaction was monitored with TLC. After the reaction was complete, the solution was filtered and the solvent was evaporated. Aqueous HCl (10%) was added to the crude product and the mixture was extracted with EtOAc (2 × 30 mL). The combined organic layers were dried over anhydrous Na₂SO₄, filtered, and the solvent was removed under reduced pressure. Purification by preparative TLC (silica gel; n-hexane-EtOAc, 3:1) gave the corres-ponding arylselenenyl-functionalized ring-opened product. All novel compounds were characterized by ^¹H and ^¹³C NMR, IR, mass spectroscopy, and elemental analysis. Compound 4e: IR (neat): 1723, 2725, 2825 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 2.06 (quin, J = 6.9 Hz, 2 H), 2.64 (t, J = 6.9 Hz, 2 H), 2.98 (t, J = 7.0 Hz, 2 H), 7.23-7.61 (m, 5 H), 9.80 (s, 1 H) ppm. ^¹³C NMR (125 MHz, CDCl₃): δ = 22.9, 27.5, 29.3, 127.5, 129.4, 129.6, 132.7, 201.8 ppm. LRMS: m/z (%) = 227 (25) [M + 2]⁺, 225 (12) [M]⁺, 185 (45), 183 (22), 171 (32), 169 (15), 157 (78), 155 (42), 123 (53), 105 (31), 91 (100), 77 (78), 71 (58), 55 (45), 41 (49). Anal. Calcd for C₁₀H₁₂OSe: C, 52.87; H, 5.32. Found: C, 52.95; H, 5.35. Compound 4f: IR (neat): 1714 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 1.96 (quin, J = 7.1 Hz, 2 H), 2.13 (s, 3 H), 2.59 (t, J = 7.0 Hz, 2 H), 2.91 (t, J = 7.2 Hz, 2 H), 7.24 (d, J = 8.5 Hz, 2 H), 7.43 (d, J = 8.5 Hz, 2 H) ppm. ^¹³C NMR (125 MHz, CDCl₃): δ = 23.9, 27.5, 30.0, 42.9, 128.2, 129.2, 133.1, 134.0, 207.7 ppm. LRMS: m/z (%) = 278 (7) [M + 4]⁺, 276 (15) [M + 2]⁺, 274 (7) [M]⁺, 191 (4), 156 (3), 125 (3), 85 (100), 43 (86). Anal. Calcd for C₁₁H₁₃ClOSe: C, 47.93; H, 4.75. Found: C, 47.83; H, 4.39. Compound 4g: mp 100-101 ˚C. IR (KBr disk): 1709, 2450-3500 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 1.99 (quin, J = 7.2 Hz, 2 H), 2.51 (t, J = 7.2 Hz, 2 H), 2.94 (t, J = 7.3 Hz, 2 H), 7.24 (d, J = 8.5 Hz, 2 H), 7.43 (d, J = 8.5 Hz, 2 H), 11.50 (br s, 1 H) ppm. ^¹³C NMR (75 MHz, CDCl₃): δ = 24.8, 27.1, 33.5, 127.7, 129.3, 133.3, 134.2, 179.3 ppm. LRMS:
m/z (%) = 280 (10) [M + 4]⁺, 278 (24) [M + 2]⁺, 276 (11) [M]⁺, 192 (21), 156 (16), 112 (24), 87 (100), 43 (44). Anal. Calcd for C₁₀H₁₁ClO₂Se: C, 43.27; H, 3.99. Found: C, 43.16; H, 3.83. Compound 4h: IR (neat): 2246 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 2.00 (quin, J = 7.0 Hz, 2 H), 2.51 (t, J = 7.0 Hz, 2 H), 2.99 (t, J = 7.1 Hz, 2 H), 7.27 (d, J = 8.5 Hz, 2 H), 7.45 (d, J = 8.5 Hz, 2 H) ppm. ^¹³C NMR (125 MHz, CDCl₃): δ = 17.1, 25.7, 26.4, 118.8, 127.0, 129.5, 133.9, 134.7 ppm. LRMS: m/z (%) = 261 (50) [M + 4]⁺, 259 (100) [M + 2]⁺, 257 (52) [M]⁺, 191 (14), 156 (14), 112 (11), 68 (14), 41 (27). Anal. Calcd for C₁₀H₁₀ClNSe: C, 46.44; H, 3.90; N, 5.42. Found: C, 46.73; H, 4.15; N, 5.58. Compound 4i: IR (neat): 1714 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 1.96 (quin, J = 7.1 Hz, 2 H), 2.13 (s, 3 H), 2.59 (t, J = 7.1 Hz, 2 H), 2.99 (t, J = 7.1 Hz, 2 H), 7.40 (t, J = 7.7 Hz, 1 H), 7.50-7.62 (m, 2 H), 7.78-7.89 (m, 3 H), 8.40 (d, J = 8.4 Hz, 1 H) ppm. ^¹³C NMR (125 MHz, CDCl₃): δ = 24.0, 27.5, 29.7, 43.1, 125.8, 126.2, 126.6, 127.5, 128.3, 128.7, 129.2, 132.3, 134.1, 134.3, 207.9 ppm. LRMS: m/z (%) = 292 (17) [M + 2]⁺, 290 (10) [M]⁺, 207 (6), 165 (6), 141 (6), 128 (15), 115 (17), 85 (100), 43 (99). Anal. Calcd for C₁₅H₁₆OSe: C, 61.86; H, 5.54. Found: C, 62.17; H, 5.76. Compound 4j: IR (neat): 1708, 2400-3500 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 2.01 (quin, J = 7.2 Hz, 2 H), 2.53 (t, J = 7.3 Hz, 2 H), 3.02 (t, J = 7.2 Hz, 2 H), 7.41 (t, J = 7.7 Hz, 1 H), 7.51-7.63 (m, 2 H), 7.80-7.90 (m, 3 H), 8.45 (d, J = 8.4 Hz, 1 H), 11.41 (br s, 1 H) ppm. ^¹³C NMR (125 MHz, CDCl₃): δ = 25.0, 27.1, 33.8, 125.8, 126.3, 126.7, 127.6, 128.5, 128.7, 129.1, 132.5, 134.1, 134.4, 179.3 ppm. LRMS: m/z (%) = 294 (87) [M + 2]⁺, 292 (47) [M]⁺, 208 (38), 141 (14), 128 (100), 115 (65), 87 (67), 43 (24). Anal. Calcd for C₁₄H₁₄O₂Se: C, 57.35; H, 4.81. Found: C, 56.99; H, 5.03.