Palladium-Catalyzed trans-Hydroalkoxylation: Counterintuitive Use of an Aryl Iodide Additive to Promote C–H Bond Formation

[Image: see text] We report an enantioselective palladium-catalyzed trans-hydroalkoxylation of propargylic amines with a trifluoroacetaldehyde-derived tether to build chiral oxazolidines. Diastereoselective hydrogenation using a heterogeneous palladium catalyst then gave access to protected benzylic...

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Autores principales: Das, Ashis, Buzzetti, Luca, Puriņš, Mikus, Waser, Jerome
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9251722/
https://www.ncbi.nlm.nih.gov/pubmed/35799768
http://dx.doi.org/10.1021/acscatal.2c01809
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author Das, Ashis
Buzzetti, Luca
Puriņš, Mikus
Waser, Jerome
author_facet Das, Ashis
Buzzetti, Luca
Puriņš, Mikus
Waser, Jerome
author_sort Das, Ashis
collection PubMed
description [Image: see text] We report an enantioselective palladium-catalyzed trans-hydroalkoxylation of propargylic amines with a trifluoroacetaldehyde-derived tether to build chiral oxazolidines. Diastereoselective hydrogenation using a heterogeneous palladium catalyst then gave access to protected benzylic amino alcohols in 45–87% yields and 84–94% ee values. Hydroalkoxylation of the alkynes required a catalytic amount of aryl iodide, highlighting the counterintuitive key role played by a putative Pd(II)/ArI oxidative addition complex to promote oxypalladation/protodemetalation.
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spelling pubmed-92517222022-07-05 Palladium-Catalyzed trans-Hydroalkoxylation: Counterintuitive Use of an Aryl Iodide Additive to Promote C–H Bond Formation Das, Ashis Buzzetti, Luca Puriņš, Mikus Waser, Jerome ACS Catal [Image: see text] We report an enantioselective palladium-catalyzed trans-hydroalkoxylation of propargylic amines with a trifluoroacetaldehyde-derived tether to build chiral oxazolidines. Diastereoselective hydrogenation using a heterogeneous palladium catalyst then gave access to protected benzylic amino alcohols in 45–87% yields and 84–94% ee values. Hydroalkoxylation of the alkynes required a catalytic amount of aryl iodide, highlighting the counterintuitive key role played by a putative Pd(II)/ArI oxidative addition complex to promote oxypalladation/protodemetalation. American Chemical Society 2022-06-13 2022-07-01 /pmc/articles/PMC9251722/ /pubmed/35799768 http://dx.doi.org/10.1021/acscatal.2c01809 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Das, Ashis
Buzzetti, Luca
Puriņš, Mikus
Waser, Jerome
Palladium-Catalyzed trans-Hydroalkoxylation: Counterintuitive Use of an Aryl Iodide Additive to Promote C–H Bond Formation
title Palladium-Catalyzed trans-Hydroalkoxylation: Counterintuitive Use of an Aryl Iodide Additive to Promote C–H Bond Formation
title_full Palladium-Catalyzed trans-Hydroalkoxylation: Counterintuitive Use of an Aryl Iodide Additive to Promote C–H Bond Formation
title_fullStr Palladium-Catalyzed trans-Hydroalkoxylation: Counterintuitive Use of an Aryl Iodide Additive to Promote C–H Bond Formation
title_full_unstemmed Palladium-Catalyzed trans-Hydroalkoxylation: Counterintuitive Use of an Aryl Iodide Additive to Promote C–H Bond Formation
title_short Palladium-Catalyzed trans-Hydroalkoxylation: Counterintuitive Use of an Aryl Iodide Additive to Promote C–H Bond Formation
title_sort palladium-catalyzed trans-hydroalkoxylation: counterintuitive use of an aryl iodide additive to promote c–h bond formation
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9251722/
https://www.ncbi.nlm.nih.gov/pubmed/35799768
http://dx.doi.org/10.1021/acscatal.2c01809
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