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

Chengyi Wang; Shaomin Deng; Rui Chen; Guohua Liu; Tanyu Cheng; Rui Liu

doi:10.1055/a-1906-3304

Synlett, Table of Contents

Synlett 2022; 33(18): 1858-1862
DOI: 10.1055/a-1906-3304

cluster

Development and Applications of Novel Ligands/Catalysts and Mechanistic Studies on Catalysis

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

Authors

Chengyi Wang‡
Shaomin Deng‡
Rui Chen
Guohua Liu
Tanyu Cheng∗
Rui Liu∗

Abstract

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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

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References

References and Notes

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16 CCDC 2156357 contains the supplementary crystallographic data for compound 2a. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via. www.ccdc.cam.ac.uk/structures
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18 Solvent-Based Reaction: Experimental Procedure A 25 mL Schlenk tube was charged with ketone 1a (224.3 mg, 1 mmol), catalyst C (31.8 mg, 0.1 mmol), 1:1 HCOOH/NEt₃ (0.28 mmol), and DCE (10 mL), and the mixture was stirred at 35 °C. During the first hour of the reaction, 0.5 mL aliquots of the solution were sampled every 15 min and then 0.5 mL aliquots were sampled every hour. Each sample of the solution was evaporated and the residue was dissolved in CDCl₃ (1 mL) containing 0.05 mmol of 1,3,5-trimethoxybenzene. [NOTE: To eliminate experimental error, the deuterated solvent should be prepared on a large scale by dissolving 1,3,5-trimethoxybenzene (5 mmol) in CDCl₃ (100 mL).] Finally, the yield of 2a was determined by ¹H NMR spectral analysis of the crude sample solution.
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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).

Supplementary Material