Mechanochemical Asymmetric Transfer Hydrogenation of Diketones to Access Chiral 1,3-Diols under Solvent-Free Conditions

Abstract

A mechanochemical asymmetric transfer hydrogenation (ATH) of diketones in the presence of a ruthenium complex under solvent-free conditions was developed to provide chiral 1,3-diol derivatives. This protocol benefits from rapid reaction kinetics, no use of solvents, and excellent enantioselectivity. In addition, the mechanochemical ATH reaction can easily be performed on a gram scale.

Key words

asymmetric catalysis - transfer hydrogenation - mechanochemistry - diols - ruthenium catalysis - solvent-free reaction

Publikationsverlauf

Eingereicht: 11. März 2022

Angenommen nach Revision: 21. Juli 2022

Accepted Manuscript online:
21. Juli 2022

Artikel online veröffentlicht:
19. August 2022

• References and Notes

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• 20 Diols 2a–p: General Procedure A 25 mL stainless steel milling vessel was charged the appropriate ketone 1 (0.2 mmol), catalyst C (0.01 mmol), 1:1 HCOOH/NEt₃ (0.056 mmol), and eight 5 mm diameter zirconia milling balls. Then the milling vessel was then placed on a planetary ball mill (900 rpm) and the mixture was milled for 45 min at approximately 35 °C. Upon completion of the reaction, the organic compounds were taken up in Et₂O. The solution was concentrated and the residue was purified by column chromatography (silica gel). (1S,3S)-1-(4-Methoxyphenyl)-3-phenylpropane-1,3-diol (2k) Purple oil; yield: 95% (99% ee, 99:1 dr) [α]_D ²⁵ = -50.2 (c 1.0, CHCl₃). HPLC [IC; hexane–i-PrOH (93:7), 1.1 mL/min, 25 °C, λ = 215 nm]: t ₁ = 18.2 min (major), t ₂ = 28.2 min, t ₃ = 29.4 min, t ₄ = 37.3 min (minor). ¹H NMR (400 MHz, DMSO-d ₆): δ = 7.32 (d, J = 2.4 Hz, 4 H), 7.28–7.18 (m, 3 H), 6.88 (d, J = 8.7 Hz, 2 H), 5.26 (d, J = 4.9 Hz, 1 H), 5.18 (d, J = 4.9 Hz, 1 H), 4.75 (m, 2 H), 3.73 (s, 3 H), 1.79 (dt, J = 8.2, 3.8 Hz, 2 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 158.5 (C), 147.2 (C), 139.1 (C), 128.5 (CH), 127.3 (CH), 127.0 (CH), 126.1 (CH), 113.9 (CH), 69.6 (CH), 69.1 (CH), 55.5 (CH₃), 50.2 (CH₂).