The Reaction of Phenyliodonium Bis(phenylsulfonyl)methylide with Alkyl Iodides

Abstract

The reactions of a β-disulfonyl iodonium ylide with alkyl iodides provided functionalized iodides via the intermediacy of ­unstable alkyliodonium ylides.

ylide - iodide - C-I insertion - alkyliodonium ylide

References

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Undergraduate Research Participant, Spring 2004.

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Representative Experimental Procedure.Synthesis of 3a: A suspension of iodonium ylide 1 (1.0 g, 2.0 mmol) and MeI (2.0 mL) in MeCN (10.0 mL) was stirred (exclusion of light) at 25 °C for 24 h. The solvent was evaporated (30 °C at 10 Torr) and the residue was chromatographed on flash silica gel (CH₂Cl₂ as eluent) to yield 0.49 g (56%) of iodide 3a as white crystals, mp 158-160 °C (lit [20] 164-165 °C). ¹H NMR (250 MHz, CDCl₃): δ = 2.52 (s, 3 H), 7.57-7.63 (m, 4 H), 7.71-7.77 (m, 2 H), 8.11-8.15 (m, 4 H). ¹³C NMR (62.5 MHz, CDCl₃): δ = 27.1, 73.9, 128.6, 132.3, 134.3, 135.1.
Synthesis of 7: A suspension of iodonium ylide 1 (1.00 g, 2.0 mmol), norbornene (1.00 g, 10.0 mmol), and MeI (2.0 mL) in dry CH₂Cl₂ (10.0 mL) was stirred (exclusion of light) at 25 °C for 24 h. The solvent was evaporated (30 °C at 10 Torr) and the residue was chromatographed on flash silica gel (CH₂Cl₂ as eluent) to yield 0.43 g (46%) of exo-iodide 7 as white crystals, mp 149-151 °C. IR (KBr): 2960, 2900, 2860, 1440, 1330, 1180, 1150, 1125, 1075, 790, 780, 750 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 1.23 (d, J = 10.6 Hz, 2 H), 1.31-1.37 (m, 1 H), 1.51-1.65 (m, 2 H), 1.84 (d, J = 10.6 Hz, 1 H), 2.34 (t, J = 7.1 Hz, 1 H), 2.80 (d, J = 3.4 Hz, 1 H), 3.13 (br s, 1 H), 4.62 (dd, J = 1.9, 7.1 Hz, 1 H), 5.42 (d, J = 7.1 Hz, 1 H), 7.44-7.48 (m, 4 H), 7.61 (t, J = 7.5 Hz, 2 H), 7.96 (t, J = 7.5 Hz, 4 H). ¹³C NMR (100 MHz, CDCl₃): δ = 32.3 (t), 36.8 (t), 40.3 (d), 44.5 (d), 48.7 (d), 49.7 (d), 93.4 (d), 128.8 (d), 129.0 (d), 129.1 (d), 129.4 (d), 134.1 (d), 134.2 (d), 134.2 (d), 138.8 (s), 140.3 (s). Anal. Calcd for C₂₀H₂₁IO₄S₂ (516.4): C, 46.52; H, 4.10; S, 12.42. Found: C, 46.52; H, 4.07; S, 12.39.

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