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Highly Enantioselective Catalytic Lactonization at Nonactivated Primary and Secondary γ-C–H Bonds

[Image: see text] Chiral oxygenated aliphatic moieties are recurrent in biological and pharmaceutically relevant molecules and constitute one of the most versatile types of functionalities for further elaboration. Herein we report a protocol for straightforward and general access to chiral γ-lactone...

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Autores principales: Call, Arnau, Capocasa, Giorgio, Palone, Andrea, Vicens, Laia, Aparicio, Eric, Choukairi Afailal, Najoua, Siakavaras, Nikos, López Saló, Maria Eugènia, Bietti, Massimo, Costas, Miquel
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10507665/
https://www.ncbi.nlm.nih.gov/pubmed/37540636
http://dx.doi.org/10.1021/jacs.3c06231
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author Call, Arnau
Capocasa, Giorgio
Palone, Andrea
Vicens, Laia
Aparicio, Eric
Choukairi Afailal, Najoua
Siakavaras, Nikos
López Saló, Maria Eugènia
Bietti, Massimo
Costas, Miquel
author_facet Call, Arnau
Capocasa, Giorgio
Palone, Andrea
Vicens, Laia
Aparicio, Eric
Choukairi Afailal, Najoua
Siakavaras, Nikos
López Saló, Maria Eugènia
Bietti, Massimo
Costas, Miquel
author_sort Call, Arnau
collection PubMed
description [Image: see text] Chiral oxygenated aliphatic moieties are recurrent in biological and pharmaceutically relevant molecules and constitute one of the most versatile types of functionalities for further elaboration. Herein we report a protocol for straightforward and general access to chiral γ-lactones via enantioselective oxidation of strong nonactivated primary and secondary C(sp(3))–H bonds in readily available carboxylic acids. The key enabling aspect is the use of robust sterically encumbered manganese catalysts that provide outstanding enantioselectivities (up to >99.9%) and yields (up to 96%) employing hydrogen peroxide as the oxidant. The resulting γ-lactones are of immediate interest for the preparation of inter alia natural products and recyclable polymeric materials.
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spelling pubmed-105076652023-09-20 Highly Enantioselective Catalytic Lactonization at Nonactivated Primary and Secondary γ-C–H Bonds Call, Arnau Capocasa, Giorgio Palone, Andrea Vicens, Laia Aparicio, Eric Choukairi Afailal, Najoua Siakavaras, Nikos López Saló, Maria Eugènia Bietti, Massimo Costas, Miquel J Am Chem Soc [Image: see text] Chiral oxygenated aliphatic moieties are recurrent in biological and pharmaceutically relevant molecules and constitute one of the most versatile types of functionalities for further elaboration. Herein we report a protocol for straightforward and general access to chiral γ-lactones via enantioselective oxidation of strong nonactivated primary and secondary C(sp(3))–H bonds in readily available carboxylic acids. The key enabling aspect is the use of robust sterically encumbered manganese catalysts that provide outstanding enantioselectivities (up to >99.9%) and yields (up to 96%) employing hydrogen peroxide as the oxidant. The resulting γ-lactones are of immediate interest for the preparation of inter alia natural products and recyclable polymeric materials. American Chemical Society 2023-08-04 /pmc/articles/PMC10507665/ /pubmed/37540636 http://dx.doi.org/10.1021/jacs.3c06231 Text en © 2023 American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/).
spellingShingle Call, Arnau
Capocasa, Giorgio
Palone, Andrea
Vicens, Laia
Aparicio, Eric
Choukairi Afailal, Najoua
Siakavaras, Nikos
López Saló, Maria Eugènia
Bietti, Massimo
Costas, Miquel
Highly Enantioselective Catalytic Lactonization at Nonactivated Primary and Secondary γ-C–H Bonds
title Highly Enantioselective Catalytic Lactonization at Nonactivated Primary and Secondary γ-C–H Bonds
title_full Highly Enantioselective Catalytic Lactonization at Nonactivated Primary and Secondary γ-C–H Bonds
title_fullStr Highly Enantioselective Catalytic Lactonization at Nonactivated Primary and Secondary γ-C–H Bonds
title_full_unstemmed Highly Enantioselective Catalytic Lactonization at Nonactivated Primary and Secondary γ-C–H Bonds
title_short Highly Enantioselective Catalytic Lactonization at Nonactivated Primary and Secondary γ-C–H Bonds
title_sort highly enantioselective catalytic lactonization at nonactivated primary and secondary γ-c–h bonds
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10507665/
https://www.ncbi.nlm.nih.gov/pubmed/37540636
http://dx.doi.org/10.1021/jacs.3c06231
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