Constructing Ar-O-P Scaffolds through Copper-Catalyzed Cleavage of the C-P Bond in BrCF2PO(OEt)2

Xi Zhang; Chengxian Hu; Lu Wang; Xue Yang; Ying Fu; Zhengyin Du

doi:10.1021/acs.joc.5c01078

Constructing Ar-O-P Scaffolds through Copper-Catalyzed Cleavage of the C-P Bond in BrCF₂PO(OEt)₂

J Org Chem. 2025 Jul 11;90(27):9608-9614. doi: 10.1021/acs.joc.5c01078. Epub 2025 Jul 1.

Authors

Xi Zhang¹, Chengxian Hu¹, Lu Wang¹, Xue Yang¹, Ying Fu¹, Zhengyin Du¹

Affiliation

¹ Key Laboratory of Eco-functional Polymer Materials of the Ministry of Education, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, P.R. China.

PMID: 40591407
DOI: 10.1021/acs.joc.5c01078

Abstract

The first example of BrCF₂PO(OEt)₂ as a phosphorylation reagent via copper-catalyzed cleavage of the C-P bond to synthesize phosphate ester products featuring Ar-O-P scaffolds from 2-phenylphenols has been developed. This protocol represents a significant departure from the conventional reactions involving BrCF₂PO(OEt)₂ in the realm of organic chemistry. Various aryl phosphate esters were prepared in up to 91% yield with exclusive chemoselectivity because no byproducts involving difluorocarbene were found. The reaction mechanism entangled diethyl iodophosphonate as a key intermediate was proposed.