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

Chengyi Wang
,
Shaomin Deng
,
Rui Chen
,
Guohua Liu
,
Tanyu Cheng
,
Rui Liu
We are grateful to the China National Natural Science Foundation (21872095, 22071154, 22001170), the Shanghai Sciences and Technologies Development Fund (20070502600), and the Shanghai Frontiers Science Center of Biomimetic Catalysis for their financial support.


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.

Supporting Information



Publication History

Received: 11 March 2022

Accepted after revision: 21 July 2022

Accepted Manuscript online:
21 July 2022

Article published online:
19 August 2022

© 2022. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 
  • References and Notes

  • 2 Thakker D, Nair S, Pagada A, Jamdade V, Malik A. Pharmacoepidemiol. Drug Saf. 2016; 25: 1131
  • 3 Chakravarti R, Sahai V. Appl. Microbiol. Biotechnol. 2004; 64: 618
  • 4 Hetzler BE, Volpin G, Vignoni E, Petrovic AG, Proni G, Hu CT, Trauner D. Angew. Chem. Int. Ed. 2018; 57: 14276
    • 5a Ohkuma T, Ooka H, Hashiguchi S, Ikariya T, Noyori R. J. Am. Chem. Soc. 1995; 117: 2675
    • 5b Hashiguchi S, Fujii A, Takehara J, Ikariya T, Noyori R. J. Am. Chem. Soc. 1995; 117: 7562
  • 6 Wang D, Astruc D. Chem. Rev. 2015; 115: 6621
  • 7 Dub PA, Gordon JC. Dalton Trans. 2016; 45: 6756
    • 8a Pan H.-J, Zhang Y, Shan C, Yu Z, Lan Y, Zhao Y. Angew. Chem. Int. Ed. 2016; 55: 9615
    • 8b Caleffi GS, Demidoff FC, Nájera C, Costa PR. R. Org. Chem. Front. 2022; 9: 1165
    • 9a Stolle A, Szuppa T, Leonhardt SE. S, Ondruschka B. Chem. Soc. Rev. 2011; 40: 2317
    • 9b Egorov IN, Santra S, Kopchuk DS, Kovalev IS, Zyryanov GV, Majee A, Ranu BC, Rusinov VL, Chupakhin ON. Green Chem. 2020; 22: 302
    • 9c Friščić T, Mottillo C, Titi HM. Angew. Chem. Int. Ed. 2020; 59: 1018
    • 9d Pérez-Venegas M, Juaristi E. ACS Sustainable Chem. Eng. 2020; 8: 8881
    • 9e Perona A, Hoyos P, Farrán Á, Hernáiz MJ. Green Chem. 2020; 22: 5559
    • 9f Ying P, Yu J, Su W. Adv. Synth. Catal. 2021; 363: 1246
  • 10 Thorwirth R, Stolle A, Ondruschka B. Green Chem. 2010; 12: 985
  • 11 Yoo K, Hong EJ, Huynh TQ, Kim B.-S, Kim JG. ACS Sustainable Chem. Eng. 2021; 9: 8679
  • 12 Ni S, Hribersek M, Baddigam SK, Ingner FJ. L, Orthaber A, Gates PJ, Pilarski LT. Angew. Chem. Int. Ed. 2021; 60: 6660
  • 13 Rodrigo E, Wiechert R, Walter MW, Braje W, Geneste H. Green Chem. 2022; 24: 1469
  • 14 Kubota K, Takahashi R, Uesugi M, Ito H. ACS Sustainable Chem. Eng. 2020; 8: 16577
    • 15a Wu L, Jin R, Li L, Hu X, Cheng T, Liu G. Org. Lett. 2017; 19: 3047
    • 15b Jin R, Zheng D, Liu R, Liu G. ChemCatChem 2018; 10: 1739
    • 15c Yang D, Wang C, Wang Y, Liu G, Cheng T, Liu R. Org. Chem. Front. 2022; 9: 102
  • 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
  • 17 Liu R, Cheng T, Kong L, Chen C, Liu G, Li H. J. Catal. 2013; 307: 55
  • 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.
  • 19 Takahashi R, Seo T, Kubota K, Ito H. ACS Catal. 2021; 11: 14803
  • 20 Diols 2ap: 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).