Synthesis of Bis(4-methylphenylsulfonimidoyl)methane – The First ‘Free’ Geminal Bis(sulfoximine)

Abstract

The synthesis of the first ‘free’ geminal bis(sulfox­imine) bis(4-methylphenylsulfonimidoyl)methane is described. Herein we present two different synthetic routes leading either to the racemate or the enantiomerically pure compound. This representative of a new substance class can be regarded as a chiral analogue of the bis(iminophosphorane)s which are used as ligands in rare-earth-metal-catalyzed hydroamination reactions.

Key words

sulfoximine - asymmetric catalysis - ligands - elimination - oxidative cleavage - sulfur - zinc - chirality

• References

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• 28 Reaction Procedure for the Zinc-Induced β-Elimination: In a Schlenk flask, zinc dust (10.1 g, 155 mmol, 12 equiv) was suspended in dry DMF (12.9 mL) and elemental iodine (6.88 g, 27.1 mmol, 2.1 equiv) was added at 0 °C. After disappearance of the brown color the brominated bis(sulfoxmine) 4 (8.00 g, 12.9 mmol), dissolved in dry DMF (32 mL), was added dropwise to the grey suspension via cannula, and the reaction mixture was stirred at 45 °C for 3 h. After complete conversion (controlled by TLC) the excess zinc was removed by filtration over a pad of Celite. The solvent was removed by vacuum distillation and freeze-drying with toluene (3 × 250 mL). The residue was taken up in CH₂Cl₂ (130 mL), the organic phase was washed with a sat. NH₄Cl solution (130 mL) and 0.1 M EDTA solution (130 mL). Drying over Na₂SO₄ and removal of the solvent delivered the crude product as a pale yellow oil. The pure bis(sulfoximine) was obtained by recrystallization from toluene (2.45g, 63%). [α]_D ²⁵ –59.1 (c 1.05, CH₂Cl₂); mp 132–133 °C (from toluene); EA calcd for C₁₃H₁₈N₂O₂S₂: C, 55.87; H, 5.63; N, 8.69; found: C, 55.79; H, 5.57; N, 8.53. ¹H NMR (500 MHz, CDCl₃): δ = 7.90 (4 H, d, J = 8.4 Hz, 4-H), 7.32 (4 H, d, J = 8.4 Hz, 3-H), 4.53 (2 H, s, 6-H), 4.12 (2 H, br s, NH), 2.43 (6 H, s, 1-H) ppm. ¹³C NMR (125 MHz, CDCl₃): δ = 145.04 (C-2), 137.18 (C-5), 129.86 (C-3), 128.89 (C-4), 77.00 (C-6), 21.59 (C-1) ppm