Intramolecular Aminotrifluoromethanesulfinyloxylation of ω-Aminoalkenes by CF₃SO₂Na/Pd(OAc)₂/PhI(OAc)₂/ ^t BuOCl/PivOH System

Published as part of the Cluster Alkene Halofunctionalization

Abstract

The first example of palladium-catalyzed intramolecular aminotrifluoromethanesulfinyloxylation of unactivated ω-aminoalkenes has been achieved. Reaction conditions are rather unique with a complex consisting of CF₃SO₂Na/Pd(OAc)₂/PhI(OAc)₂/ ^t BuOCl/PivOH to provide 6-endo-cyclized type products with a piperidine skeleton. Yields are moderate, and SO₂ is not extruded. This method also provides the first synthesis of 3-trifluoromethanesulfinyloxy piperidine derivatives.

Key words

amination - alkenes - cyclization - fluorine - halogenation - sulfur - palladium

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• 18 General Procedure To a stirring mixture of ω-aminoalkenes 1 (0.1 mmol), PIDA (64.2 mg, 0.2 mmol, 2.0 equiv), Pd(OAc)₂ (2.2 mg, 0.01 mmol, 10 mol%), CF₃SO₂Na (78.0 mg, 0.5 mmol, 5.0 equiv), and PivOH (51.0 mg, 0.5 mmol, 5.0 equiv) in MeCN (0.5 mL, 0.2 M) at 10 °C, ^t BuOCl (10.9 mg, 11 μL, 0.1 mmol, 1.0 equiv) was added under nitrogen atmosphere. The mixture was stirred at room temperature for 15 h. The resulting mixture was cooled to 0 °C, quenched with sat. NaHCO₃ aqueous solution, and extracted with EtOAc three times. The combined organic layer was washed with brine, dried with Na₂SO_4, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (benzene/EtOAc = 98:2) to give product 3. 5,5-Dimethyl-1-tosylpiperidin-3-yl Trifluoromethanesulfinate (3a) 60% yield (dr = 54:46, mixture of diastereoisomer at sulfur atom); white solid.¹H NMR (300 MHz, CDCl₃): δ = 7.64 (q, J = 3.2 Hz, 2 H), 7.36–7.33 (m, 2 H), 4.82–4.68 (m, 1 H), 4.00 (q, J = 5.4 Hz, 0.5 H), 3.85 (q, J = 5.4 Hz, 0.5 H), 3.28 (d, J = 11.5 Hz, 0.5 H), 3.20 (d, J = 11.5 Hz, 0.5 H), 2.44 (s, 3 H), 2.37–2.30 (m, 1 H), 2.18 (d, J = 11.5 Hz, 0.5 H), 2.10 (d, J = 11.5 Hz, 0.5 H), 1.87 (td, J = 12.1, 4.6 Hz, 1 H), 1.43–1.26 (m, 1 H), 1.11 (s, 1.5 H), 1.10 (s, 1.5 H), 1.01 (s, 1.5 H), 0.99 (s, 1.5 H). ¹⁹F NMR (282 MHz, CDCl₃): δ = –80.0 (major, s), –80.2 (minor, s). ¹³C NMR (176 MHz, CDCl₃): δ = 143.9, 133.2, 129.8, 127.4, 127.3, 122.5 (q, J = 336.9 Hz), 122.4 (q, J = 336.0 Hz), 56.4, 56.3, 50.1, 50.0, 43.8, 43.5, 32.4, 32.3, 28.0, 27.9, 26.9, 24.9, 24.7, 21.4. IR (KBr) 2962, 2928, 1470, 1346, 1196, 1159, 1129, 950, 907, 857, 677 cm^–1. ESI-MS: m/z = 422 [M + Na]⁺. ESI-HRMS: m/z calcd for C₁₅H₂₀NO₄F₃NaS₂: 422.0684; found: 422.0679.
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• 20 The ¹⁹F NMR (282 MHz) spectra of the mixture of CF₃SO₂Na (1.0 equiv), PivOH (1.0 equiv), and ^t BuOCl (1.0 equiv) in CD₃CN indicated two singlet signals at δ = –74.01 ppm (CF₃SO₂Cl) and –77.14 ppm (7).
• 21 The¹⁹F NMR (282 MHz) spectra of the mixture of 6 (1.0 equiv) and CF₃SO₂Na (1.0 equiv) in CD₃CN indicated three singlet signals at δ = –73.98 ppm (CF₃SO₂Cl), –77.14 ppm (7), and –83.00 ppm (CF₃SO₂Na).