Direct Aryloxylation/Alkyloxylation of Dialkyl Phosphonates for the Synthesis of Mixed Phosphonates

Hai Huang; Johanna Denne; Chou-Hsun Yang; Haobin Wang; Jun Yong Kang

doi:10.1002/anie.201802082

Direct Aryloxylation/Alkyloxylation of Dialkyl Phosphonates for the Synthesis of Mixed Phosphonates

Angew Chem Int Ed Engl. 2018 May 28;57(22):6624-6628. doi: 10.1002/anie.201802082. Epub 2018 May 7.

Authors

Hai Huang¹, Johanna Denne², Chou-Hsun Yang², Haobin Wang², Jun Yong Kang¹

Affiliations

¹ Department of Chemistry and Biochemistry, University of Nevada Las Vegas, 4505 South Maryland Parkway, Las Vegas, NV, 89154-4003, USA.
² Department of Chemistry, University of Colorado Denver, Denver, CO, 80217-3364, USA.

PMID: 29660223
DOI: 10.1002/anie.201802082

Abstract

A strategy for the direct functionalization strategy of inertial dialkyl phosphonates with hydroxy compounds to afford diverse mixed phosphonates with good yields and functional-group tolerance has been developed. Mechanistic investigations involving both NMR studies and DFT studies suggest that an unprecedented highly reactive P^V species (phosphoryl pyridin-1-ium salt), a key intermediate for this new synthetic transformation, is generated in situ from dialkyl phosphonate in the presence of Tf₂ O/pyridine.

Keywords: DFT study; alkyloxylation; aryloxylation; phosphonates; phosphoryl pyridin-1-ium.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.