Amine-Free O-Sulfonylation by a Combination of 4-Methylpyridine N-Oxide Catalyst with 4Å Molecular Sieves

Abstract

An amine-free sulfonylation of various alcohols was developed that uses 4-methylpyridine N-oxide in the presence of 4Å molecular sieves at room temperature. This mild method gives various sulfonylated products in high yields, and can be applied to base-sensitive substrates.

Key words

sulfonylation - methylpyridine oxide - alcohols - molecular sieves - sulfonates - mesylation

Publication History

Received: 11 May 2022

Accepted after revision: 31 May 2022

Accepted Manuscript online:
31 May 2022

Article published online:
23 June 2022

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• 19 (–)-Menthol Mesylate (2a); Typical Procedure MsCl (49.8 μL, 1.09 mmol, 1.7 equiv) was added to a stirred suspension of (–)-menthol (1; 100 mg, 0.640 mmol, 1.0 equiv), 7 (13.8 mg, 20 mol%), and MS 4A (300 mg; 300 wt% of 1) in CH₂Cl₂ (0.8 mL), and the mixture was stirred at rt for 2 h. The reaction was then quenched with 1 M aq HCl (10 mL), and the mixture was extracted with Et₂O (3 × 10 mL). The combined extracts were washed with H₂O (30 mL) and sat. brine (30 mL) then dried and concentrated under reduced pressure. The residue was purified by column chromatography [silica gel, CH₂Cl₂–hexane (2:1)] to give a colorless oil; yield: 147 mg (98%). ¹H NMR (600 MHz, CDCl₃): δ = 0.86 (d, J = 6.6 Hz, 3 H), 0.89 (m, 1 H), 0.93 (d, J = 6.6, Hz, 3 H), 0.94 (d, J = 6.6 Hz, 3 H), 1.06 (m, 1 H), 1.29 (q, J = 12.0 Hz, 1 H), 1.42 (m, 1 H), 1.49 (m, 1 H), 1.65–1.75 (m, 2 H), 2.07 (m, 1 H), 2.26 (m, 1 H), 2.94 (s, 3 H), 4.55 (dt, J = 4.8, 10.8 Hz, 1 H). ¹³C NMR (150 MHz, CDCl₃): δ = 15.7, 20.8, 21.8, 23.1, 25.8, 31.6, 33.8, 39.1, 42.2, 47.4, 83.4.