A Mn(II)-Catalyzed Tandem Oxidative Cleavage and Ammoxidation of Alcohols to Primary Amides

Abstract

The cleavage/functionalization of C–C bonds in alcohols has emerged as a robust tool for exploration of new conversion. Herein, a Mn(OAc)₂-catalyzed oxidative cleavage/ammoxidation of a wide range of alcohols to amides has been developed. The practicality of this transformation was demonstrated by a scale-up experiment and an amidation of mixed alcohols in a one-pot fashion. Moreover, a plausible mechanism was proposed based on a series of control experiments.

Key words

alcohols - amides - manganese catalysis - tandem reactions - C–C bond cleavage - ammoxidation

• References and Notes

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• 17 General Procedure for Oxidative Cleavage and Amidation Reactions: An oven-dried tube was charged with alcohols (0.5 mmol), Mn(OAc)₂ (0.25 mmol), KI (0.025 mmol), (NH₄)₂CO₃ (1.0 mmol), and DMSO (1 mL). The tube was attached inside an autoclave, and the reaction was carried out at 150 °C (bath temperature) in 1.0 MPa of O₂. After the reaction was completed under the indicated time period, the appropriate amount of dichloromethane and methanol was added to the reaction mixture and ultrasound for 3 min. Then the solvent was removed in vacuo. The residue was purified by flash column chromatography on silica gel using the indicated solvent system to afford the product benzamides.
• 18 Benzamide (1): According to general procedure to afford 1 (46.5 mg, 77%) as a white solid (flash column chromatography using gradient elution: 10% to 50% ethyl acetate in hexanes). ¹H NMR (400 MHz, DMSO-d₆ ): δ = 7.97 (s, 1 H), 7.92–7.82 (m, 2 H), 7.56–7.48 (m, 1 H), 7.48–7.40 (m, 2 H), 7.36 (s, 1 H). ¹³C NMR (101 MHz, DMSO-d₆ ): δ = 167.87, 134.22, 131.17, 128.16, 127.41.