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

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. Additionally, 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 Tf 2O/pyridine.

Authors:
 [1];  [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Nevada, Las Vegas, NV (United States). Dept. of Chemistry and Biochemistry
  2. Univ. of Colorado, Denver, CO (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1543471
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 57; Journal Issue: 22; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; alkyloxylation; aryloxylation; DFT study; phosphates; phosphoryl pyridin-1-ium

Citation Formats

Huang, Hai, Denne, Johanna, Yang, Chou-Hsun, Wang, Haobin, and Kang, Jun Yong. Direct Aryloxylation/Alkyloxylation of Dialkyl Phosphonates for the Synthesis of Mixed Phosphonates. United States: N. p., 2018. Web. doi:10.1002/anie.201802082.
Huang, Hai, Denne, Johanna, Yang, Chou-Hsun, Wang, Haobin, & Kang, Jun Yong. Direct Aryloxylation/Alkyloxylation of Dialkyl Phosphonates for the Synthesis of Mixed Phosphonates. United States. doi:10.1002/anie.201802082.
Huang, Hai, Denne, Johanna, Yang, Chou-Hsun, Wang, Haobin, and Kang, Jun Yong. Mon . "Direct Aryloxylation/Alkyloxylation of Dialkyl Phosphonates for the Synthesis of Mixed Phosphonates". United States. doi:10.1002/anie.201802082. https://www.osti.gov/servlets/purl/1543471.
@article{osti_1543471,
title = {Direct Aryloxylation/Alkyloxylation of Dialkyl Phosphonates for the Synthesis of Mixed Phosphonates},
author = {Huang, Hai and Denne, Johanna and Yang, Chou-Hsun and Wang, Haobin and Kang, Jun Yong},
abstractNote = {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. Additionally, mechanistic investigations involving both NMR studies and DFT studies suggest that an unprecedented highly reactive PV 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 Tf2O/pyridine.},
doi = {10.1002/anie.201802082},
journal = {Angewandte Chemie (International Edition)},
number = 22,
volume = 57,
place = {United States},
year = {2018},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 9 works
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Figures / Tables:

Figure 1 Figure 1: Examples of pharmaceutically-relevant mixed alkyl aryl phosphonates

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