A Chiral Pentafluorinated Isopropyl Group via Iodine(I)/(III) Catalysis

An I(I)/(III) catalysis strategy to construct an enantioenriched fluorinated isostere of the (i)Pr group is reported. The difluorination of readily accessible α‐CF(3)‐styrenes is enabled by the in situ generation of a chiral ArIF(2) species to forge a stereocentre with the substituents F, CH(2)F and...

Descripción completa

Detalles Bibliográficos
Autores principales: Meyer, Stephanie, Häfliger, Joel, Schäfer, Michael, Molloy, John J., Daniliuc, Constantin G., Gilmour, Ryan
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7986799/
https://www.ncbi.nlm.nih.gov/pubmed/33427355
http://dx.doi.org/10.1002/anie.202015946
_version_ 1783668515195060224
author Meyer, Stephanie
Häfliger, Joel
Schäfer, Michael
Molloy, John J.
Daniliuc, Constantin G.
Gilmour, Ryan
author_facet Meyer, Stephanie
Häfliger, Joel
Schäfer, Michael
Molloy, John J.
Daniliuc, Constantin G.
Gilmour, Ryan
author_sort Meyer, Stephanie
collection PubMed
description An I(I)/(III) catalysis strategy to construct an enantioenriched fluorinated isostere of the (i)Pr group is reported. The difluorination of readily accessible α‐CF(3)‐styrenes is enabled by the in situ generation of a chiral ArIF(2) species to forge a stereocentre with the substituents F, CH(2)F and CF(3) (up to 95 %, >20:1 vicinal:geminal difluorination). The replacement of the metabolically labile benzylic proton results in a highly preorganised scaffold as was determined by X‐ray crystallography (π→σ* and stereoelectronic gauche σ→σ* interactions). A process of catalyst editing is disclosed in which preliminary validation of enantioselectivity is placed on a structural foundation.
format Online
Article
Text
id pubmed-7986799
institution National Center for Biotechnology Information
language English
publishDate 2021
publisher John Wiley and Sons Inc.
record_format MEDLINE/PubMed
spelling pubmed-79867992021-03-25 A Chiral Pentafluorinated Isopropyl Group via Iodine(I)/(III) Catalysis Meyer, Stephanie Häfliger, Joel Schäfer, Michael Molloy, John J. Daniliuc, Constantin G. Gilmour, Ryan Angew Chem Int Ed Engl Communications An I(I)/(III) catalysis strategy to construct an enantioenriched fluorinated isostere of the (i)Pr group is reported. The difluorination of readily accessible α‐CF(3)‐styrenes is enabled by the in situ generation of a chiral ArIF(2) species to forge a stereocentre with the substituents F, CH(2)F and CF(3) (up to 95 %, >20:1 vicinal:geminal difluorination). The replacement of the metabolically labile benzylic proton results in a highly preorganised scaffold as was determined by X‐ray crystallography (π→σ* and stereoelectronic gauche σ→σ* interactions). A process of catalyst editing is disclosed in which preliminary validation of enantioselectivity is placed on a structural foundation. John Wiley and Sons Inc. 2021-02-09 2021-03-15 /pmc/articles/PMC7986799/ /pubmed/33427355 http://dx.doi.org/10.1002/anie.202015946 Text en © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Communications
Meyer, Stephanie
Häfliger, Joel
Schäfer, Michael
Molloy, John J.
Daniliuc, Constantin G.
Gilmour, Ryan
A Chiral Pentafluorinated Isopropyl Group via Iodine(I)/(III) Catalysis
title A Chiral Pentafluorinated Isopropyl Group via Iodine(I)/(III) Catalysis
title_full A Chiral Pentafluorinated Isopropyl Group via Iodine(I)/(III) Catalysis
title_fullStr A Chiral Pentafluorinated Isopropyl Group via Iodine(I)/(III) Catalysis
title_full_unstemmed A Chiral Pentafluorinated Isopropyl Group via Iodine(I)/(III) Catalysis
title_short A Chiral Pentafluorinated Isopropyl Group via Iodine(I)/(III) Catalysis
title_sort chiral pentafluorinated isopropyl group via iodine(i)/(iii) catalysis
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7986799/
https://www.ncbi.nlm.nih.gov/pubmed/33427355
http://dx.doi.org/10.1002/anie.202015946
work_keys_str_mv AT meyerstephanie achiralpentafluorinatedisopropylgroupviaiodineiiiicatalysis
AT hafligerjoel achiralpentafluorinatedisopropylgroupviaiodineiiiicatalysis
AT schafermichael achiralpentafluorinatedisopropylgroupviaiodineiiiicatalysis
AT molloyjohnj achiralpentafluorinatedisopropylgroupviaiodineiiiicatalysis
AT daniliucconstanting achiralpentafluorinatedisopropylgroupviaiodineiiiicatalysis
AT gilmourryan achiralpentafluorinatedisopropylgroupviaiodineiiiicatalysis
AT meyerstephanie chiralpentafluorinatedisopropylgroupviaiodineiiiicatalysis
AT hafligerjoel chiralpentafluorinatedisopropylgroupviaiodineiiiicatalysis
AT schafermichael chiralpentafluorinatedisopropylgroupviaiodineiiiicatalysis
AT molloyjohnj chiralpentafluorinatedisopropylgroupviaiodineiiiicatalysis
AT daniliucconstanting chiralpentafluorinatedisopropylgroupviaiodineiiiicatalysis
AT gilmourryan chiralpentafluorinatedisopropylgroupviaiodineiiiicatalysis

Ejemplares similares