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.
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.
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
18Solvent-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
