Stoichiometric Release of SO₂ from Adducts: Application to the Direct Synthesis of Protected Dienes

Abstract

The in situ, stoichiometric release of SO₂ was studied from DABSO (DABCO adduct with SO₂) and DMAP adduct. When involved in cheletropic additions, free SO₂ released by this technique proved much more reactive than its adducts. Some examples of applications towards the direct synthesis of protected dienes from allylic alcohols are given.

Key words

sulfur dioxide - dienes - sulfolenes

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• 13 A dry tube was charged with 4-(dimethylamino)-1-sulfano-pyridinium inner salt (DMAP·SO₂, 1.68 g, 9.0 mmol) and sealed under nitrogen. Dry MeCN (8 mL) was added. After 5 min stirring at r.t., 2-(4-methoxyphenyl)but-3-en-2-ol (519 μL, 3.0 mmol) was added, and the reaction was stirred at r.t. during 15 min. To the resulting solution was added dropwise at 0 °C over a period of 5 min, freshly distilled MeSO₂Cl (1.16 mL, 9.0 mmol). The ice bath was removed, and the temperature gradually rose to r.t. The sealed tube was heated to 70 °C for 12 h. After cooling, the solvent was removed in vacuo. The crude product was purified on silica gel, using PE–EtOAc (7:3) as an eluent to afford pure compound as a colorless powder (499 mg, 74%). R_f = 0.47 (PE–EtOAc, 1:1); mp 150–151 °C. IR: ν = 3393, 3088, 2980, 1591, 1470, 1432, 1365, 1293, 1188, 1129, 1074, 995, 923, 788, 750, 688, 629, 488 cm^–1. ¹H NMR (300 MHz, CDCl₃): δ = 7.30 (d, 2 H, ³ J_H–H  = 8.8 Hz), 6.91 (d, 2 H, ³ J_H–H  = 8.8 Hz,), 6.21 (m, 1 H), 4.11 (m, 2 H), 4.01 (s, 2 H), 3.82 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 160.5, 135.8, 126.9, 126.7, 115.0, 114.4, 57.8, 56.79, 55.6. Anal Calcd for C₁₁H₁₂O₃S: C, 58.91; H, 5.39. Found: C, 59.34; H, 5.52. HRMS (ESI⁺): m/z [M + H]⁺ calcd for C₁₁H₁₃O₃S: 225.0585; found: 225.0578.