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Synthesis of highly substituted allenylsilanes by alkylidenation of silylketenes

BACKGROUND: Allenylsilanes are useful intermediates in organic synthesis. An attractive, convergent but little used approach for their synthesis is the alkylidenation of stable silylketenes. Reactions thus far have been limited to the use of unsubstituted silylketenes (or equivalents) with stabilise...

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Autores principales: Marsden, Stephen P, Ducept, Pascal C
Formato: Texto
Lenguaje:English
Publicado: Beilstein-Institut 2005
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC1399453/
https://www.ncbi.nlm.nih.gov/pubmed/16542018
http://dx.doi.org/10.1186/1860-5397-1-5
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author Marsden, Stephen P
Ducept, Pascal C
author_facet Marsden, Stephen P
Ducept, Pascal C
author_sort Marsden, Stephen P
collection PubMed
description BACKGROUND: Allenylsilanes are useful intermediates in organic synthesis. An attractive, convergent but little used approach for their synthesis is the alkylidenation of stable silylketenes. Reactions thus far have been limited to the use of unsubstituted silylketenes (or equivalents) with stabilised or semi-stabilised ylides only. The current study explores the reactions of substituted ketenes prepared through rhodium(II)-mediated rearrangement of silylated diazoketones. RESULTS: A range of novel 1,3-disubstituted and 1,3,3-trisubstituted allenylsilanes were prepared using stabilised and semi-stabilised ylides. Alkylidenation with non-stabilised phosphorus ylides was not viable, but the use of titanium-based methylenating reagents was successful, allowing access to 1-substituted allenylsilanes. CONCLUSION: Many novel allenylsilanes may be accessed by alkylidenation of substituted silylketenes. Importantly, for the first time, simple methylenation of silylketenes has been achieved using titanium carbenoid-based reagents.
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spelling pubmed-13994532006-03-13 Synthesis of highly substituted allenylsilanes by alkylidenation of silylketenes Marsden, Stephen P Ducept, Pascal C Beilstein J Org Chem Full Research Paper BACKGROUND: Allenylsilanes are useful intermediates in organic synthesis. An attractive, convergent but little used approach for their synthesis is the alkylidenation of stable silylketenes. Reactions thus far have been limited to the use of unsubstituted silylketenes (or equivalents) with stabilised or semi-stabilised ylides only. The current study explores the reactions of substituted ketenes prepared through rhodium(II)-mediated rearrangement of silylated diazoketones. RESULTS: A range of novel 1,3-disubstituted and 1,3,3-trisubstituted allenylsilanes were prepared using stabilised and semi-stabilised ylides. Alkylidenation with non-stabilised phosphorus ylides was not viable, but the use of titanium-based methylenating reagents was successful, allowing access to 1-substituted allenylsilanes. CONCLUSION: Many novel allenylsilanes may be accessed by alkylidenation of substituted silylketenes. Importantly, for the first time, simple methylenation of silylketenes has been achieved using titanium carbenoid-based reagents. Beilstein-Institut 2005-08-26 /pmc/articles/PMC1399453/ /pubmed/16542018 http://dx.doi.org/10.1186/1860-5397-1-5 Text en Copyright © 2005, Marsden and Ducept https://creativecommons.org/licenses/by/2.0https://www.beilstein-journals.org/bjoc/termsThis is an Open Access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (https://www.beilstein-journals.org/bjoc/terms)
spellingShingle Full Research Paper
Marsden, Stephen P
Ducept, Pascal C
Synthesis of highly substituted allenylsilanes by alkylidenation of silylketenes
title Synthesis of highly substituted allenylsilanes by alkylidenation of silylketenes
title_full Synthesis of highly substituted allenylsilanes by alkylidenation of silylketenes
title_fullStr Synthesis of highly substituted allenylsilanes by alkylidenation of silylketenes
title_full_unstemmed Synthesis of highly substituted allenylsilanes by alkylidenation of silylketenes
title_short Synthesis of highly substituted allenylsilanes by alkylidenation of silylketenes
title_sort synthesis of highly substituted allenylsilanes by alkylidenation of silylketenes
topic Full Research Paper
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC1399453/
https://www.ncbi.nlm.nih.gov/pubmed/16542018
http://dx.doi.org/10.1186/1860-5397-1-5
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