Highly Active Manganese-Mediated Acylation of Alcohols with Acid Chlorides or Anhydrides

Abstract

To explore further the practical uses of highly active manganese (Mn*), a variety of alcohols were treated with Mn*, and the resulting complexes were coupled with acid chlorides and/or acetic anhydride in the absence of any extra catalyst. The subsequent reactions took place smoothly under mild conditions, providing the corresponding O-acylation products in good to excellent isolated yields.

Key words

active manganese - manganese catalysis - acylation - ­alcohols - thiols - esters

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• 10 Phenyl 3-Chlorobenzoate (1c); Typical Procedure A 25 mL flask was charged with lithium (0.07 g, 9.68 mmol), naphthalene (0.19 g, 1.48 mmol), anhyd MnI₂ (1.45 g, 4.71 mmol), and freshly distilled THF (10 mL) under argon pressure, and the mixture was stirred for 1 h at r.t. To the resulting slurry, containing 2.5 mmol of highly active manganese, was added PhOH (0.47 g, 5.0 mmol) and the resulting mixture was stirred at r.t. for 10 min. Neat 3-chlorobenzoyl chloride (0.88 g, 5.0 mmol) was then added to the flask, and the mixture was stirred at r.t. for 30 min. The reaction was then quenched with 3 M aq HCl, and the mixture was extracted with Et₂O (3 × 10 mL). The organic layers were combined and washed with sat. aq NaHCO₃ (3 × 10 mL), sat. aq Na₂S₂O₃ (3 × 10 mL), and brine (3 × 10 mL), then dried (MgSO₄). Column chromatography (silica gel, 1% EtOAc–hexanes) gave a pale-yellow solid; yield: 0.96 g (83%); mp 60–63 °C. ¹H NMR (500 MHz, CDCl₃): δ = 8.19 (br s, 1 H), 8.10 (d, J = 8.0 Hz, 1 H), 7.64 (d, J = 8.0 Hz, 1 H), 7.50–7.45 (m, 3 H), 7.32 (t, J = 7.5 Hz, 1 H), 7.24 (d, J = 7.5 Hz, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 164.0, 150.7, 134.8, 133.6, 131.3, 130.2, 130.0, 129.6, 128.3, 126.2, 121.6. HRMS: m/z [M⁺] calcd for C₁₃H₉ClO₂: 232.0291; Found: 232.0280.