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On the Configurational Stability of Chiral Heteroatom-Substituted [D(1)]Methylpalladium Complexes as Intermediates of Stille and Suzuki–Miyaura Cross-Coupling Reactions
Enantiomerically pure (S)-tributylstannyl[D(1)]methanol and (R)- and (S)-tributylstannyl[D(1)]methyl benzoates were Stille-coupled with bromobenzene and benzoyl chloride in 1,4-dioxane and toluene using [(Ph(3)P)(4)Pd] or [(Ph(3)P)(2)PdCl(2)] either alone or in combination with CuCN as cocatalyst at...
Autores principales: | , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
WILEY-VCH Verlag
2013
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3790956/ https://www.ncbi.nlm.nih.gov/pubmed/24115906 http://dx.doi.org/10.1002/ejoc.201300439 |
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author | Malova Krizkova, Petra Hammerschmidt, Friedrich |
author_facet | Malova Krizkova, Petra Hammerschmidt, Friedrich |
author_sort | Malova Krizkova, Petra |
collection | PubMed |
description | Enantiomerically pure (S)-tributylstannyl[D(1)]methanol and (R)- and (S)-tributylstannyl[D(1)]methyl benzoates were Stille-coupled with bromobenzene and benzoyl chloride in 1,4-dioxane and toluene using [(Ph(3)P)(4)Pd] or [(Ph(3)P)(2)PdCl(2)] either alone or in combination with CuCN as cocatalyst at temperatures up to 80 °C. The products were found to be enantiomerically pure. (R)- and (S)-N-(tributylstannyl[D(1)]methyl)phthalimides gave enantiomerically pure products with benzoyl chloride, but with bromobenzene protected phenyl[D(1)]methylamines gave products of only 52–69 % ee depending on the solvent used. Tributyl(thio[D(1)]methyl)stannanes could not be Stille-coupled with benzoyl chloride or with bromobenzene. Similarly, dimethyl phenyl[D(1)]methylboronate underwent a Suzuki–Miyaura coupling with bromobenzene to give phenyl[D(1)]methylsilane with 99 % ee. All couplings followed a retentive course and, except in one case, the intermediate [XCHDPdL(n)] complexes were found to be microscopically configurationally stable. |
format | Online Article Text |
id | pubmed-3790956 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2013 |
publisher | WILEY-VCH Verlag |
record_format | MEDLINE/PubMed |
spelling | pubmed-37909562013-10-08 On the Configurational Stability of Chiral Heteroatom-Substituted [D(1)]Methylpalladium Complexes as Intermediates of Stille and Suzuki–Miyaura Cross-Coupling Reactions Malova Krizkova, Petra Hammerschmidt, Friedrich European J Org Chem Full Papers Enantiomerically pure (S)-tributylstannyl[D(1)]methanol and (R)- and (S)-tributylstannyl[D(1)]methyl benzoates were Stille-coupled with bromobenzene and benzoyl chloride in 1,4-dioxane and toluene using [(Ph(3)P)(4)Pd] or [(Ph(3)P)(2)PdCl(2)] either alone or in combination with CuCN as cocatalyst at temperatures up to 80 °C. The products were found to be enantiomerically pure. (R)- and (S)-N-(tributylstannyl[D(1)]methyl)phthalimides gave enantiomerically pure products with benzoyl chloride, but with bromobenzene protected phenyl[D(1)]methylamines gave products of only 52–69 % ee depending on the solvent used. Tributyl(thio[D(1)]methyl)stannanes could not be Stille-coupled with benzoyl chloride or with bromobenzene. Similarly, dimethyl phenyl[D(1)]methylboronate underwent a Suzuki–Miyaura coupling with bromobenzene to give phenyl[D(1)]methylsilane with 99 % ee. All couplings followed a retentive course and, except in one case, the intermediate [XCHDPdL(n)] complexes were found to be microscopically configurationally stable. WILEY-VCH Verlag 2013-08 2013-06-27 /pmc/articles/PMC3790956/ /pubmed/24115906 http://dx.doi.org/10.1002/ejoc.201300439 Text en © 2013 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA. http://creativecommons.org/licenses/by/2.5/ Re-use of this article is permitted in accordance with the Creative Commons Deed, Attribution 2.5, which does not permit commercial exploitation. |
spellingShingle | Full Papers Malova Krizkova, Petra Hammerschmidt, Friedrich On the Configurational Stability of Chiral Heteroatom-Substituted [D(1)]Methylpalladium Complexes as Intermediates of Stille and Suzuki–Miyaura Cross-Coupling Reactions |
title | On the Configurational Stability of Chiral Heteroatom-Substituted [D(1)]Methylpalladium Complexes as Intermediates of Stille and Suzuki–Miyaura Cross-Coupling Reactions |
title_full | On the Configurational Stability of Chiral Heteroatom-Substituted [D(1)]Methylpalladium Complexes as Intermediates of Stille and Suzuki–Miyaura Cross-Coupling Reactions |
title_fullStr | On the Configurational Stability of Chiral Heteroatom-Substituted [D(1)]Methylpalladium Complexes as Intermediates of Stille and Suzuki–Miyaura Cross-Coupling Reactions |
title_full_unstemmed | On the Configurational Stability of Chiral Heteroatom-Substituted [D(1)]Methylpalladium Complexes as Intermediates of Stille and Suzuki–Miyaura Cross-Coupling Reactions |
title_short | On the Configurational Stability of Chiral Heteroatom-Substituted [D(1)]Methylpalladium Complexes as Intermediates of Stille and Suzuki–Miyaura Cross-Coupling Reactions |
title_sort | on the configurational stability of chiral heteroatom-substituted [d(1)]methylpalladium complexes as intermediates of stille and suzuki–miyaura cross-coupling reactions |
topic | Full Papers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3790956/ https://www.ncbi.nlm.nih.gov/pubmed/24115906 http://dx.doi.org/10.1002/ejoc.201300439 |
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