Acridine-Based SNS–Ruthenium Pincer Complex-Catalyzed Borrowing Hydrogen-Mediated C–C Alkylation Reaction: Application to the Guerbet Reaction

Abstract

SNS-based ruthenium pincer catalysts were applied in a Guerbet condensation reaction of primary alcohols to give β-alkylated dimeric alcohols in good yields. The ability of these complexes to convert ethanol into butanol was also investigated. The work was then extended toward the C-alkylation of secondary alcohols with primary alcohols to give α-alkylated ketones. Several control experiments showed the involvement of borrowing hydrogen in the protocol.

Key words

borrowing hydrogen reaction - ruthenium catalysis - alcohols - Guerbet reaction - ketones - butanol

Publication History

Received: 20 April 2022

Accepted after revision: 12 June 2022

Accepted Manuscript online:
12 June 2022

Article published online:
08 July 2022

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• 24 2-Ethylhexan-1-ol (5a); Typical Procedure An oven-dried 15 mL pressure tube was charged with BuOH (4 mmol), catalyst 1 (0.5 mol%), and NaOH (25 mol%), and the mixture was purged three times with argon. The tube was sealed with a screw cap and the mixture was heated at 135 °C for 36 h. The resulting mixture was passed through a plug of Celite and then all the volatiles were evaporated. The crude mixture was then purified by column chromatography [silica gel (100–200 mesh)] to give a colorless liquid; yield: 195 mg (75%). ¹H NMR (600 MHz, CDCl₃): δ = 3.54 (d, J = 5.2 Hz, 2 H), 1.44–1.16 (m, 9 H), 0.89 (m, 6 H). ¹³C NMR (150 MHz, CDCl₃): δ = 65.4, 42.1, 30.2, 29.2, 23.4, 23.2, 14.2, 11.2.
• 25 1,3-Diphenylpropan-1-one (8a); Typical Procedure An oven-dried 15 ml pressure tube was charged with PhCH(Me)OH (1 mmol), BzOH (1 mmol) catalyst 1 (0.5 mol%) and NaOH (25 mol% with respect to both alcohols), and the mixture was purged three times with argon. The tube was sealed with a screw cap and heated at 135 °C for 36 h. The resulting mixture was passed through a plug of Celite and then all the volatiles were evaporated. The crude mixture was then purified by column chromatography [silica gel (100–200 mesh)] to give a white solid; yield: 157 mg (75%). ¹H NMR (600 MHz, CDCl₃): δ = 7.99 (t, J = 6.7 Hz, 2 H), 7.59 (d, J = 6.8 Hz, 1 H), 7.49 (d, J = 7.6 Hz, 2 H), 7.33 (t, J = 6.7 Hz, 2 H), 7.33–7.23 (m, 2 H), 7.26–7.22 (m, 1 H), 3.35 (t, J = 7.5 Hz, 2 H), 3.11 (t, J = 7.5 Hz, 2 H). ¹³C NMR (150 MHz, CDCl₃): δ = 199.4, 141.4, 137.0, 133.2, 128.7, 128.7, 128.6, 128.6, 128.2, 126.3, 40.6, 30.3.