Facile Synthesis of Stereodefined α-Iodovinyl Sulfoxides, Versatile Platform to Trisubstituted Olefins

Abstract

Stereodefined α-iodovinyl sulfoxides bearing a sulfinyl group and an iodo group were prepared by a one-pot iodination/Horner–Wadsworth–Emmons reaction protocol. This reaction can be applied to a wide range of aldehydes, and further application was demonstrated.

Key words

sulfoxides - vinyl iodide - vinyl sulfoxides - sulfinyl phosphonates - trisubstituted olefins - olefination - Horner–Wadsworth–Emmons reaction - halovinyl sulfoxides

• References and Notes

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Use of a bulky phosphonate tends to increase the Z selectivity. This fact suggests that formation of the oxaphosphetane intermediate and/or elimination of the phosphate become slow presumably due to the steric hindrance around the phosphorus atom. Therefore, a thermodynamically controlled product is preferably obtained. For related examples see:
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For related examples of the NMR analyses of tri- or tetrasubstituted α-iodovinyl sulfoxide, see:
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One-pot iodination and HWE reaction was hinted by:
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• 14 This reaction is exothermic, therefore, the reaction was conducted in water bath for the large-scale reaction.
• 15 Typical Procedure of One-Pot Iodination–HWE Reaction In a two-necked round-bottomed flask was placed LiCl (44.7 mg, 0.314 mmol), to which a solution of sulfinyl-phosphonate 3b (100 mg, 0.314 mmol) in MeCN (1 mL) and TBD (87.4 mg, 0.628 mmol) or DBU (94.0 μL, 0.628 mmol) was added successively at room temperature. The mixture was stirred, and I₂ (solid, 79.7 mg, 0.314 mmol) was added in several portions. The mixture turned into an orange color solution. After stirring for 10 min, a solution of benzaldehyde (9, 22.2 mg, 0.209 mmol) in MeCN (1 mL) was added slowly, and the stirring was continued for 5 min at room temperature. The reaction was quenched by adding 10% Na₂S₂O₃ aqueous solution, the products were extracted with EtOAc (3×), and the combined organic extracts were washed with brine, dried (Na₂SO₄), and concentrated in vacuo. The residue was purified by flash column chromatography (hexane–EtOAc = 2:1) to obtain 10 in 71% yield (Z/E = 95:5, TBD) or 78% yield (Z/E = 77:23, DBU). Recrystallization (EtOAc–hexane = 2:1) gave pure ( Z )-10 as colorless needles. Analytical Data for ( Z )-10: R_f = 0.74 (hexane–EtOAc = 2:3); mp 84–86 °C. ¹H NMR (600 MHz, CDCl₃): δ = 2.41 (s, 3 H), 7.31 (d, 2 H, J = 8.1 Hz), 7.41–7.42 (m, 3 H), 7.60 (d, 2 H, J = 8.1 Hz), 7.77 (dd, 2 H, J = 6.5, 2.8 Hz), 8.16 (s, 1 H). ¹³C NMR (150 MHz, CDCl₃): δ = 21.5, 110.3, 126.0, 128.4, 129.2, 129.9, 130.0, 134.1, 138.9, 139.8, 142.3. IR (neat): 3052, 3023, 2973, 2920, 2865, 2360, 2342, 1593, 1491, 1445, 1397, 1266, 1178, 1084, 1059, 925, 872, 808, 749, 692 cm^–1. [α]_D ²⁰ +22.3 (c 1.11, CHCl₃). HRMS (ESI-TOF): m/z calcd for C₁₅H₁₄IOS [M + H]⁺: 368.9805; found: 368.9807. Anal. Calcd for C₁₅H₁₃IOS: C, 48.93; H, 3.56; S, 8.71. Found: C, 48.96; H, 3.53; S, 8.52.
• 16 Attempt for the reaction with acetophenone also failed, resulting in the formation of many unidentified byproducts.
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