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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

phosphine oxides


ID: J48-Y2022