Synthesis and Reactions of the First Fluorine-Containing 1,3-Bis(trimethyl­silyloxy)-1,3-butadienes

Abstract

The first fluorine-containing 1,3-bis(silyl enol ethers), 2-fluoro-1,3-bis(trimethylsilyloxy)-1,3-butadienes, have been prepared. Their reaction with electrophiles allows a convenient synthesis of various open-chain and cyclic organofluorine compounds which are not readily available by other methods.

Key words

arenes - organofluorine compounds - regioselectivity - silyl enol ethers

References and Notes

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19

CCDC 684861 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

21

Synthesis of 2-Ethoxy-3-fluoro-6-(phenylsulfonyl)pyr-idin-4-ol (14): To phenylsulfonyl cyanide was dropwise added 3a at -78 ˚C. The neat reaction mixture was subsequently stirred at 45 ˚C for 48 h. To the mixture was added a sat. aq solution of NH₄Cl (20 mL) and the organic and the aqueous layer were separated. The latter was extracted with CH₂Cl₂ (3 × 20 mL). The combined organic layers were dried (Na₂SO₄), filtered and the filtrate was concentrated in vacuo. The residue was purified by chromatography (silica gel, heptanes-EtOAc) to give 14. Starting with phenylsulfonyl cyanide (0.167 g, 1.0 mmol) and 3a (0.589 g, 2.0 mmol), 14 was isolated as a red solid (0.179 g, 59%). ^¹H NMR (250 MHz, CDCl₃): δ = 1.22 (t, ^³ J = 7.1 Hz, 3 H, OCH₂CH ₃), 4.26 (q, ^³ J = 7.0 Hz, 2 H, OCH ₂CH₃), 7.19 (br s, 1 H, OH_heter), 7.43 (m, 1 H, CH_heter), 7.46-7.50 (m, 2 H, CH_Ph), 7.53-7.56 (m, 1 H, CH_Ph), 7.95 (dd, ^³ J = 8.4 Hz, ⁴ J = 1.5 Hz, 2 H, CH_Ph). ^¹³C NMR (75 MHz, CDCl₃): δ = 14.1 (OCH₂ CH₃), 63.6 (OCH₂CH₃), 107.8 (CH_heter), 128.9 (2 × CH_Ph), 129.0 (2 × CH_Ph), 133.8 (CH_Ph), 136.8 (d, ^¹ J = 252.4 Hz, CF_heter), 138.4 (C_Ph), 149.4 (d, ⁴ J = 6.7 Hz, C_heter), 151.3 (d, ^² J = 10.2 Hz, COH_heter), 153.8 (d, ^² J = 9.9 Hz, C_heter). ^¹9F NMR (235 MHz, CDCl₃): δ =
-162.05 (CF_heter). IR (neat): 3354 (w), 1576 (m), 1440 (m), 1353 (m), 1317 (m), 1149 (s), 1076 (m), 1022 (m), 740 (s), 724 (s), 682 (s), 585 (s) cm^-¹. HRMS (ESI, positive): m/z
[M + H]⁺ calcd for C₁₃H₁₃FNO₄S: 298.05438; found: 298.05413. HRMS (ESI, positive): m/z [M + Na]⁺ calcd for C₁₃H₁₂FNO₄SNa: 320.03652; found: 320.03633. All products gave satisfactory spectroscopic data and correct elemental analyses and/or high resolution mass data.