Thiopropenoylstannanes: The First Access to the Class of Thioacylstannanes

Abstract

Reaction of stannylated allenes with bis(trimethyl­silyl)sulfide/CoCl₂·6H₂O affords the first example of the synthesis of thioacylstannanes. The so obtained thiopropenoylstannanes behave as efficient thiabutadienes towards different in situ generated thioaldehydes and thioacylsilanes, leading to 2-substituted 4-stannyl-1,3-dithiacyclohex-4-ene derivatives through a regioselective hetero Diels-Alder reaction.

thioacylstannanes - thioacylsilanes - cycloadditions - heterodynes - dithiins

References

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14

Typical Procedure: A solution of 50 mg (0.17 mmol) of allene 1a and 72 µL (0.34 mmol, 61 mg) of HMDST in 0.7 mL of THF was slowly added at -78 °C under inert atmosphere with a solution of CoCl₂·6H₂O (40 mg, 0.17 mmol) in 2 mL of THF. The mixture was kept at -78 °C for 4 h, the progress of the reaction monitored by TLC, then allowed to reach r.t. After dilution with Et₂O and washing with H₂O, the organic phase was dried over Na₂SO₄. Evaporation of the solvent and purification on TLC (hexanes-Et₂O 40:1) afforded 25 mg of 4a (49%) together with 12% of 5a. Compound 4a: ¹H NMR (200 MHz, CDCl₃): δ = 0.23 (9 H, s), 1.59 (3 H, d, J = 7.0 Hz), 3.24 (1 H, dd, J = 6.2 Hz, J = 17.4 Hz), 3.58 (1 H, bdd, J = 3.1 Hz, J = 17.4 Hz), 4.25 (1 H, q, J = 7.0 Hz), 5.95 (1 H, dd, J = 3.1 Hz, J = 6.2 Hz) ppm. ¹³C NMR (50 MHz, CDCl₃): δ = -2.3, 20.9, 29.7, 30.3, 122.2, 125.5 ppm. MS: m/z (%) = 296 (8) [M⁺], 281 (4), 221 (19), 165 (79), 135 (22), 71 (100). Compound 5a: ¹H NMR (200 MHz, CDCl₃): d = 1.49 (3 H, d, J = 7.2 Hz), 3.25 (1 H, ddd, J = 1.4 Hz, J = 5.8 Hz, J = 18.0 Hz), 3.51 (1 H, ddd, J = 2.2 Hz, J = 3.4 Hz, J = 18.0 Hz), 4.20 (1 H, q, J = 7.2 Hz), 5.89 (1 H, ddd, J = 3.4 Hz, J = 5.8 Hz, J = 10.6 Hz), 6.21 (1 H, ddd, J = 1.4 Hz, J = 2.2 Hz, J = 10.6 Hz) ppm. ¹³C NMR (50 MHz, CDCl₃): d = 21.9, 25.2, 40.6, 121.9, 137.0 ppm.

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16

General Procedure: To a solution of 50 mg (0.17 mmol) of allene 1a in 1.5 mL of THF were added, under N₂ atmosphere, 151 mg (0.85 mmol) of benzoyltrimethylsilane 7b ¹⁸ and 426 µL (2.04 mmol, 363 mg) of HMDST. The mixture was cooled to -78 °C and added with a solution of 243 mg (1.02 mmol) of CoCl₂·6H₂O dissolved in 6.0 mL of THF. Progress of the reaction was monitored by TLC (hexanes-Et₂O 40:1) and after 1.5 h at -78 °C the mixture was allowed to reach r.t. (ca. 15 °C), then diluted with Et₂O and the organic phase washed with H₂O and brine, and dried over Na₂SO₄. Evaporation of the solvent afforded the crude product. Purification on Florisil (hexanes-Et₂O 40:1) afforded 23 mg of 9b (32%) and 8 mg of 1,2-dithiin isomer 11 (11%), together with minor amounts of the corresponding destannylated compounds (ca. 10%). Compound 9b: ¹H NMR (200 MHz, CDCl₃): d = 0.17 (9 H, s), 0.23 (9 H, s), 2.94 (1 H, dd, J = 6.2 Hz, J = 19.0 Hz), 3.08 (1 H, dd, J = 3.0 Hz, J = 19.0 Hz), 6.03 (1 H, dd, J = 3.0 Hz, J = 6.2 Hz), 6.96-7.90 (5 H, m) ppm. ¹³C NMR (50 MHz, CDCl₃):
δ = -3.6, -2.7, 22.9, 47.2, 125.7, 127.5, 127.8, 128.3, 128.8, 141.5 ppm. MS: m/z (%) = 267 (6) [M⁺ - 163], 194 (8), 161 (11), 77 (19) 73 (100). Compound 11: ¹H NMR (200 MHz, CDCl₃): d = 0.03 (9 H, s), 0.10 (9 H, s), 2.50-2.30 (2 H, m), 5.92 (1 H, dd, J = 3.1 Hz, J = 6.0 Hz), 7.01-7.90 (5 H, m) ppm. ¹³C NMR (50 MHz, CDCl₃): d = -3.7, -1.7, 40.1, 46.5, 125.5, 127.1, 128.0, 128.2, 128.5, 140.5 ppm. MS:
m/z (%) = 327 (21) [M⁺ - 103], 179 (13), 165 (10), 135 (32), 121 (28), 103 (27), 73 (100).

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