1,2-Diarylethenyl Sulfones: Readily-Prepared Masked Diarylethynes for Access to Aryleneethynylenes

Abstract

1,2-Di(halophenyl)ethenyl phenyl sulfones were prepared readily by successive treatment of halophenylmethyl sulfones with LiHMDS (lithium hexamethyldisilazide), halobenzaldehydes, diethyl chlorophosphate and LiHMDS. The di(halophenyl)ethenyl sulfones thus obtained were transformed successfully to aryleneethynylenes by Sonogashira coupling with arylethyne followed by LiHMDS-promoted elimination of phenylsulfinic acid.

alkynes - sulfones - aldehydes - eliminations - aryleneethynylenes

References and Notes

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Typical Procedures1-(3-Bromophenyl)-2-(3-iodophenyl)-1-(phenylsulfon-yl)ethene (4a): To a THF solution (30 mL) of 3-bromo-phenylmethyl phenyl sulfone (2.00 g, 6.4 mmol) was added a THF solution of LiHMDS (1.0 M, 7.0 mL, 7.0 mmol) at -78 °C, and the mixture was stirred for 0.5 h. A THF solution (8 mL) of 3-iodobenzaldehyde (1.24 g, 5.3 mmol) was added at -78 °C, and the mixture was stirred for 1 h. Diethyl chlorophosphate (0.75 mL, 5.4 mmol) was added at -78 °C, and the mixture was stirred at r.t. for 1 h. A THF solution of LiHMDS (1.0 M, 5.4 mL, 5.4 mmol) was added at -78 °C, and the mixture was stirred at r.t. overnight. After usual workup with EtOAc-aq NH₄Cl, the organic layer was evaporated, and the residue was subjected to column chromatography on silica gel (10% EtOAc-hexane) to furnish 4a (2.24 g, 80%).Compound 4a: E/Z = 88:12 (the geometry of E- or Z-isomers was not determined, several signals overlapped in ¹³C NMR). ¹H NMR (500 MHz, CDCl₃): δ = 6.91 (t, J = 7.8 Hz, 1 H), 6.93-7.00, 7.03-7.12 (m, 2 H), 7.13-7.21, 7.32-7.37 (m, 2 H), 7.40-7.68 (m, 8 H), 7.85, 7.88 (s, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 94.1 (93.5), 122.7 (122.1), 128.7, 128.9, 129.1, 129.3, 128.1, 128.5, 128.6, 130.1, 130.4, 129.5, 129.7, 132.5, 132.9, 133.3, 133.6, 134.5, 132.1, 132.7, 133.4, 135.3, 136.4, 138.1, 139.0, 139.6, 137.1, 137.3, 137.6, 139.9, 141.6, 141.7.
1-(3-Bromophenyl)-2-[3-(4-methoxyphenyl-ethynyl)phenyl]-1-(phenylsulfonyl)ethene (5a): A toluene solution (14 mL) of 4a (1.20 g, 2.3 mmol), 4-methoxy-phenylethyne (341 mg, 2.6 mmol), Pd(PPh₃)₄ (132 mg, 0.11 mmol), CuI (23.0 mg, 0.12 mmol) and diisopropylamine (4.6 mL) was stirred at r.t. for 12 h. After filtration, the filtrate was washed with aq NH₄Cl, and the aqueous layer was extracted with EtOAc. The combined organic layer was washed with aq NaCl, dried over MgSO₄ and evaporated. The residue was subjected to column chromatography on silica gel (10% EtOAc-hexane) to afford 5a (1.07 g, 88%). Compound 5a: only one isomer was obtained. The geometry E or Z isomer was not determined. ¹H NMR (500 MHz, CDCl₃): δ = 3.83 (s, 3 H), 6.87 (d, J = 8.9 Hz, 2 H), 6.90 (d, J = 8.2 Hz, 1 H), 6.97 (d, J = 7.9 Hz, 1 H), 7.12 (t, J = 7.8 Hz, 1 H), 7.14-7.18 (m, 2 H), 7.29 (s, 1 H), 7.37-7.46 (m, 5 H), 7.49-7.53 (m, 1 H), 7.57 (t, J = 7.5 Hz, 1 H), 7.64 (d, J = 7.6 Hz, 2 H), 7.94 (s, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 55.3, 86.9, 90.4, 114.1, 114.9, 122.6, 124.4, 128.6, 128.7, 128.9, 129.0, 129.5, 130.3, 132.4, 132.6, 132.9, 133.1, 133.2, 133.4, 133.5, 133.9, 137.5, 138.3, 141.0, 159.9.
1-(3-Bromophenylethynyl)-3-(4-methoxyphenyl-ethynyl)benzene (3a): To a toluene solution (22 mL) of 5a (285 mg, 0.54 mmol) was added a THF solution of LiHMDS (1.0 M, 2.2 mL, 2.2 mmol) at 0 °C, and the mixture was stirred at r.t. for 2 h. After usual workup with EtOAc-aq NH₄Cl, the organic layer was evaporated, and the residue was subjected to column chromatography on silica gel (2% EtOAc-hexanes) to furnish 3a (161 mg, 77%). Compound 3a: ¹H NMR (500 MHz, CDCl₃): δ = 3.84 (s, 3 H), 6.89 (d, J = 8.9 Hz, 2 H), 7.23 (t, J = 7.9 Hz, 1 H), 7.33 (t, J = 7.8 Hz, 1 H), 7.43-7.50 (m, 6 H), 7.67-7.70 (m, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 55.2, 87.1, 88.2, 89.9, 90.2, 114.0, 115.0, 122.1, 123.0, 124.0, 125.0, 128.4, 129.7, 130.1, 130.9, 131.4, 131.5, 133.1, 134.3, 134.4, 159.7.