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Pre-electrolysis of LiClO(4) in Acetonitrile: Electrochemically Induced Protolytic Carbon–Carbon Bond Formation of Benzylic Ethers and Acetals with Allyl Trimethylsilane and Other Carbon Nucleophiles

[Image: see text] The pre-electrolysis of LiClO(4) in acetonitrile in an undivided cell applying only “catalytic” amounts of current (e.g., 0.05 F) led to the formation of a strong acidic medium for the activation of benzylic ethers and acetals. The activated primary and secondary benzylic ethers an...

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Autores principales: Fastie, Cornelius, Li, Luomo, Bätcher, Moritz, Hilt, Gerhard
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10476155/
https://www.ncbi.nlm.nih.gov/pubmed/37594465
http://dx.doi.org/10.1021/acs.joc.3c01256
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author Fastie, Cornelius
Li, Luomo
Bätcher, Moritz
Hilt, Gerhard
author_facet Fastie, Cornelius
Li, Luomo
Bätcher, Moritz
Hilt, Gerhard
author_sort Fastie, Cornelius
collection PubMed
description [Image: see text] The pre-electrolysis of LiClO(4) in acetonitrile in an undivided cell applying only “catalytic” amounts of current (e.g., 0.05 F) led to the formation of a strong acidic medium for the activation of benzylic ethers and acetals. The activated primary and secondary benzylic ethers and acetals could be converted with a range of carbon nucleophiles, such as allyl trimethylsilane, silyl enol ethers, and enol acetates, for the formation of new carbon–carbon bonds. A chemoselective reaction was observed when electron-deficient benzylic acetals were converted with allyl trimethylsilane to the monoallylated products, whereas an electron-rich benzylic acetal led to the double allylated product under activation of both ether groups.
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spelling pubmed-104761552023-09-05 Pre-electrolysis of LiClO(4) in Acetonitrile: Electrochemically Induced Protolytic Carbon–Carbon Bond Formation of Benzylic Ethers and Acetals with Allyl Trimethylsilane and Other Carbon Nucleophiles Fastie, Cornelius Li, Luomo Bätcher, Moritz Hilt, Gerhard J Org Chem [Image: see text] The pre-electrolysis of LiClO(4) in acetonitrile in an undivided cell applying only “catalytic” amounts of current (e.g., 0.05 F) led to the formation of a strong acidic medium for the activation of benzylic ethers and acetals. The activated primary and secondary benzylic ethers and acetals could be converted with a range of carbon nucleophiles, such as allyl trimethylsilane, silyl enol ethers, and enol acetates, for the formation of new carbon–carbon bonds. A chemoselective reaction was observed when electron-deficient benzylic acetals were converted with allyl trimethylsilane to the monoallylated products, whereas an electron-rich benzylic acetal led to the double allylated product under activation of both ether groups. American Chemical Society 2023-08-18 /pmc/articles/PMC10476155/ /pubmed/37594465 http://dx.doi.org/10.1021/acs.joc.3c01256 Text en © 2023 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 Fastie, Cornelius
Li, Luomo
Bätcher, Moritz
Hilt, Gerhard
Pre-electrolysis of LiClO(4) in Acetonitrile: Electrochemically Induced Protolytic Carbon–Carbon Bond Formation of Benzylic Ethers and Acetals with Allyl Trimethylsilane and Other Carbon Nucleophiles
title Pre-electrolysis of LiClO(4) in Acetonitrile: Electrochemically Induced Protolytic Carbon–Carbon Bond Formation of Benzylic Ethers and Acetals with Allyl Trimethylsilane and Other Carbon Nucleophiles
title_full Pre-electrolysis of LiClO(4) in Acetonitrile: Electrochemically Induced Protolytic Carbon–Carbon Bond Formation of Benzylic Ethers and Acetals with Allyl Trimethylsilane and Other Carbon Nucleophiles
title_fullStr Pre-electrolysis of LiClO(4) in Acetonitrile: Electrochemically Induced Protolytic Carbon–Carbon Bond Formation of Benzylic Ethers and Acetals with Allyl Trimethylsilane and Other Carbon Nucleophiles
title_full_unstemmed Pre-electrolysis of LiClO(4) in Acetonitrile: Electrochemically Induced Protolytic Carbon–Carbon Bond Formation of Benzylic Ethers and Acetals with Allyl Trimethylsilane and Other Carbon Nucleophiles
title_short Pre-electrolysis of LiClO(4) in Acetonitrile: Electrochemically Induced Protolytic Carbon–Carbon Bond Formation of Benzylic Ethers and Acetals with Allyl Trimethylsilane and Other Carbon Nucleophiles
title_sort pre-electrolysis of liclo(4) in acetonitrile: electrochemically induced protolytic carbon–carbon bond formation of benzylic ethers and acetals with allyl trimethylsilane and other carbon nucleophiles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10476155/
https://www.ncbi.nlm.nih.gov/pubmed/37594465
http://dx.doi.org/10.1021/acs.joc.3c01256
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