Rh-Catalyzed Regio- and Enantioselective Allylic Phosphinylation
Bing Li, Min Liu, Sajid Ur Rehman and Changkun Li*
*School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China, Email: chklisjtu.edu.cn
B. Li, M. Liu, S. U. Rehman, C. Li, J. Am. Chem. Soc., 2022, 144, 2893-2898.
DOI: 10.1021/jacs.2c00239
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Abstract
In a Rh-catalyzed highly regio- and enantioselective synthesis of allylic phosphine oxides in the presence of a chiral bisoxazoline-phosphine ligand, the use of α-hydroxylalkylphosphine oxides as substrates to keep a low concentration of the secondary phosphine oxides is essential for the high yields.
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General Procedure for Synthesis of Allylic Phosphine Oxides
In a N2-filled glovebox, a pressure tube equipped with a magnetic stir bar was charged with Rh(cod)2BF4 (1.0 mg, 1.25 mol%), ligand (1.3 mg, 1.3 mol%), (PhO)2PO2H (5.0 mg, 10.0 mol%), toluene (0.5 mL) and CH3CN (0.05 mL). The reaction mixture was stirred at room temperature for 15 minutes. Allylic alcohol (0.2 mmol, 1.0 eq) and α-hydroxylalkylphosphine oxide (0.24 mmol, 1.2 eq) were added to the above solution. The tube was tightly capped, transferred out of the glovebox and heated at 100°C for 24 hours. After cooling down, the crude mixture was concentrated and the residue was purified by column chromatography to get the corresponding allylic phosphine oxides.
Key Words
ID: J48-Y2022