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Phosphonate–Phosphinate Rearrangement
[Image: see text] LiTMP metalated dimethyl N-Boc-phosphoramidates derived from 1-phenylethylamine and 1,2,3,4-tetrahydronaphthalen-1-ylamine highly selectively at the CH(3)O group to generate short-lived oxymethyllithiums. These isomerized to diastereomeric hydroxymethylphosphonamidates (phosphate–p...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2014
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4301053/ https://www.ncbi.nlm.nih.gov/pubmed/25525945 http://dx.doi.org/10.1021/jo502567j |
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author | Qian, Renzhe Roller, Alexander Hammerschmidt, Friedrich |
author_facet | Qian, Renzhe Roller, Alexander Hammerschmidt, Friedrich |
author_sort | Qian, Renzhe |
collection | PubMed |
description | [Image: see text] LiTMP metalated dimethyl N-Boc-phosphoramidates derived from 1-phenylethylamine and 1,2,3,4-tetrahydronaphthalen-1-ylamine highly selectively at the CH(3)O group to generate short-lived oxymethyllithiums. These isomerized to diastereomeric hydroxymethylphosphonamidates (phosphate–phosphonate rearrangement). However, s-BuLi converted the dimethyl N-Boc-phosphoramidate derived from 1-phenylethylamine to the N-Boc α-aminophosphonate preferentially. Only s-BuLi deprotonated dimethyl hydroxymethylphosphonamidates at the benzylic position and dimethyl N-Boc α-aminophosphonates at the CH(3)O group to induce phosphonate–phosphinate rearrangements. In the former case, the migration of the phosphorus substituent from the nitrogen to the carbon atom followed a retentive course with some racemization because of the involvement of a benzyllithium as an intermediate. |
format | Online Article Text |
id | pubmed-4301053 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2014 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-43010532015-01-21 Phosphonate–Phosphinate Rearrangement Qian, Renzhe Roller, Alexander Hammerschmidt, Friedrich J Org Chem [Image: see text] LiTMP metalated dimethyl N-Boc-phosphoramidates derived from 1-phenylethylamine and 1,2,3,4-tetrahydronaphthalen-1-ylamine highly selectively at the CH(3)O group to generate short-lived oxymethyllithiums. These isomerized to diastereomeric hydroxymethylphosphonamidates (phosphate–phosphonate rearrangement). However, s-BuLi converted the dimethyl N-Boc-phosphoramidate derived from 1-phenylethylamine to the N-Boc α-aminophosphonate preferentially. Only s-BuLi deprotonated dimethyl hydroxymethylphosphonamidates at the benzylic position and dimethyl N-Boc α-aminophosphonates at the CH(3)O group to induce phosphonate–phosphinate rearrangements. In the former case, the migration of the phosphorus substituent from the nitrogen to the carbon atom followed a retentive course with some racemization because of the involvement of a benzyllithium as an intermediate. American Chemical Society 2014-12-19 2015-01-16 /pmc/articles/PMC4301053/ /pubmed/25525945 http://dx.doi.org/10.1021/jo502567j Text en Copyright © 2014 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. |
spellingShingle | Qian, Renzhe Roller, Alexander Hammerschmidt, Friedrich Phosphonate–Phosphinate Rearrangement |
title | Phosphonate–Phosphinate
Rearrangement |
title_full | Phosphonate–Phosphinate
Rearrangement |
title_fullStr | Phosphonate–Phosphinate
Rearrangement |
title_full_unstemmed | Phosphonate–Phosphinate
Rearrangement |
title_short | Phosphonate–Phosphinate
Rearrangement |
title_sort | phosphonate–phosphinate
rearrangement |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4301053/ https://www.ncbi.nlm.nih.gov/pubmed/25525945 http://dx.doi.org/10.1021/jo502567j |
work_keys_str_mv | AT qianrenzhe phosphonatephosphinaterearrangement AT rolleralexander phosphonatephosphinaterearrangement AT hammerschmidtfriedrich phosphonatephosphinaterearrangement |