Synthesis of Five-Membered Cyclic Phosphinic Acids via the [4C+1P] Cyclization of 1,3-Dienes with a Combination of PBr3 and P(OMe)3 as the P(III) Source

Ang Li; Fu-She Han

doi:10.1021/acs.joc.3c00567

Synthesis of Five-Membered Cyclic Phosphinic Acids via the [4C+1P] Cyclization of 1,3-Dienes with a Combination of PBr₃ and P(OMe)₃ as the P^(III) Source

J Org Chem. 2023 Sep 1;88(17):12224-12235. doi: 10.1021/acs.joc.3c00567. Epub 2023 Aug 10.

Authors

Ang Li^{1

2}, Fu-She Han^{1

2}

Affiliations

¹ Jilin Province Key Lab of Green Chemistry and Process, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun, Jilin 130022, China.
² School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, Anhui, China.

PMID: 37561550
DOI: 10.1021/acs.joc.3c00567

Abstract

An efficient method for the synthesis of 1-hydroxy-2,5-dihydrophosphole 1-oxides, a type of five-membered P-containing heterocyclic compound, is presented. The reaction was carried out through a [4C+1P] cyclization of 1,3-dienes with a combination of PBr₃ and P(OMe)₃ as the P^(III) source. To compare with the reported methods, the protocol reported herein not only is much milder and more rapid but also displays a broad substrate scope and affords the products in high yields (50-94%). In addition, the reaction could be reliably scaled up at the gram-scale level and was demonstrated to be a versatile platform for flexible derivatization. Consequently, this method provides a general and reliable way for the synthesis of five-membered phosphole derivatives.