Conformationally Locked Pyramidality Explains the Diastereoselectivity in the Methylation of trans-Fused Butyrolactones

[Image: see text] A stereoselectivity model inspired by the total synthesis of stemona alkaloids is developed to explain why enolate-derived 3,4-fused butyrolactones are methylated with a preference for syn alkylation. The model shows how conformational locking present in nonplanar enolate structure...

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Autores principales: Csókás, Dániel, Siitonen, Juha H., Pihko, Petri M., Pápai, Imre
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2020
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7309317/
https://www.ncbi.nlm.nih.gov/pubmed/32338517
http://dx.doi.org/10.1021/acs.orglett.0c01008
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author Csókás, Dániel
Siitonen, Juha H.
Pihko, Petri M.
Pápai, Imre
author_facet Csókás, Dániel
Siitonen, Juha H.
Pihko, Petri M.
Pápai, Imre
author_sort Csókás, Dániel
collection PubMed
description [Image: see text] A stereoselectivity model inspired by the total synthesis of stemona alkaloids is developed to explain why enolate-derived 3,4-fused butyrolactones are methylated with a preference for syn alkylation. The model shows how conformational locking present in nonplanar enolate structures favors syn over anti methylation, due to less significant structural distortions in the syn pathway. The developed model was also successfully used to rationalize selectivities of previously documented methylation reactions.
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spelling pubmed-73093172020-06-23 Conformationally Locked Pyramidality Explains the Diastereoselectivity in the Methylation of trans-Fused Butyrolactones Csókás, Dániel Siitonen, Juha H. Pihko, Petri M. Pápai, Imre Org Lett [Image: see text] A stereoselectivity model inspired by the total synthesis of stemona alkaloids is developed to explain why enolate-derived 3,4-fused butyrolactones are methylated with a preference for syn alkylation. The model shows how conformational locking present in nonplanar enolate structures favors syn over anti methylation, due to less significant structural distortions in the syn pathway. The developed model was also successfully used to rationalize selectivities of previously documented methylation reactions. American Chemical Society 2020-04-27 2020-06-19 /pmc/articles/PMC7309317/ /pubmed/32338517 http://dx.doi.org/10.1021/acs.orglett.0c01008 Text en Copyright © 2020 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 Csókás, Dániel
Siitonen, Juha H.
Pihko, Petri M.
Pápai, Imre
Conformationally Locked Pyramidality Explains the Diastereoselectivity in the Methylation of trans-Fused Butyrolactones
title Conformationally Locked Pyramidality Explains the Diastereoselectivity in the Methylation of trans-Fused Butyrolactones
title_full Conformationally Locked Pyramidality Explains the Diastereoselectivity in the Methylation of trans-Fused Butyrolactones
title_fullStr Conformationally Locked Pyramidality Explains the Diastereoselectivity in the Methylation of trans-Fused Butyrolactones
title_full_unstemmed Conformationally Locked Pyramidality Explains the Diastereoselectivity in the Methylation of trans-Fused Butyrolactones
title_short Conformationally Locked Pyramidality Explains the Diastereoselectivity in the Methylation of trans-Fused Butyrolactones
title_sort conformationally locked pyramidality explains the diastereoselectivity in the methylation of trans-fused butyrolactones
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7309317/
https://www.ncbi.nlm.nih.gov/pubmed/32338517
http://dx.doi.org/10.1021/acs.orglett.0c01008
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