Copper(I)-Catalyzed Synthesis of Unsymmetrical All-Carbon Bis-Quaternary Centers at the Opposing α-Carbons of Cyclohexanones

[Image: see text] We describe a new synthetic reaction that generates all-carbon bis-quaternary centers at the opposing side of α-carbons in cyclohexanone with four different substituents in a controlled manner. Catalyzed by Cu(MeCN)(4)BF(4) salt, this chemistry is proposed to proceed via an interme...

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Autores principales: Malone, Joshua A., Philkhana, Satish Chandra, Stepherson, Jacob R., Badmus, Fatimat O., Fronczek, Frank R., Kartika, Rendy
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9490817/
https://www.ncbi.nlm.nih.gov/pubmed/35767696
http://dx.doi.org/10.1021/acs.orglett.2c01890
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author Malone, Joshua A.
Philkhana, Satish Chandra
Stepherson, Jacob R.
Badmus, Fatimat O.
Fronczek, Frank R.
Kartika, Rendy
author_facet Malone, Joshua A.
Philkhana, Satish Chandra
Stepherson, Jacob R.
Badmus, Fatimat O.
Fronczek, Frank R.
Kartika, Rendy
author_sort Malone, Joshua A.
collection PubMed
description [Image: see text] We describe a new synthetic reaction that generates all-carbon bis-quaternary centers at the opposing side of α-carbons in cyclohexanone with four different substituents in a controlled manner. Catalyzed by Cu(MeCN)(4)BF(4) salt, this chemistry is proposed to proceed via an intermediacy of unsymmetrical O-allyl oxyallyl cations, which undergo a sequence of regioselective nucleophilic addition with substituted indoles and diastereoselective Claisen rearrangement in a single synthetic operation. The stereochemical outcome of the products features the cis diastereorelationship between the two aryl groups at the α,α′-positions.
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spelling pubmed-94908172022-09-22 Copper(I)-Catalyzed Synthesis of Unsymmetrical All-Carbon Bis-Quaternary Centers at the Opposing α-Carbons of Cyclohexanones Malone, Joshua A. Philkhana, Satish Chandra Stepherson, Jacob R. Badmus, Fatimat O. Fronczek, Frank R. Kartika, Rendy Org Lett [Image: see text] We describe a new synthetic reaction that generates all-carbon bis-quaternary centers at the opposing side of α-carbons in cyclohexanone with four different substituents in a controlled manner. Catalyzed by Cu(MeCN)(4)BF(4) salt, this chemistry is proposed to proceed via an intermediacy of unsymmetrical O-allyl oxyallyl cations, which undergo a sequence of regioselective nucleophilic addition with substituted indoles and diastereoselective Claisen rearrangement in a single synthetic operation. The stereochemical outcome of the products features the cis diastereorelationship between the two aryl groups at the α,α′-positions. American Chemical Society 2022-06-29 2022-07-08 /pmc/articles/PMC9490817/ /pubmed/35767696 http://dx.doi.org/10.1021/acs.orglett.2c01890 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 Malone, Joshua A.
Philkhana, Satish Chandra
Stepherson, Jacob R.
Badmus, Fatimat O.
Fronczek, Frank R.
Kartika, Rendy
Copper(I)-Catalyzed Synthesis of Unsymmetrical All-Carbon Bis-Quaternary Centers at the Opposing α-Carbons of Cyclohexanones
title Copper(I)-Catalyzed Synthesis of Unsymmetrical All-Carbon Bis-Quaternary Centers at the Opposing α-Carbons of Cyclohexanones
title_full Copper(I)-Catalyzed Synthesis of Unsymmetrical All-Carbon Bis-Quaternary Centers at the Opposing α-Carbons of Cyclohexanones
title_fullStr Copper(I)-Catalyzed Synthesis of Unsymmetrical All-Carbon Bis-Quaternary Centers at the Opposing α-Carbons of Cyclohexanones
title_full_unstemmed Copper(I)-Catalyzed Synthesis of Unsymmetrical All-Carbon Bis-Quaternary Centers at the Opposing α-Carbons of Cyclohexanones
title_short Copper(I)-Catalyzed Synthesis of Unsymmetrical All-Carbon Bis-Quaternary Centers at the Opposing α-Carbons of Cyclohexanones
title_sort copper(i)-catalyzed synthesis of unsymmetrical all-carbon bis-quaternary centers at the opposing α-carbons of cyclohexanones
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9490817/
https://www.ncbi.nlm.nih.gov/pubmed/35767696
http://dx.doi.org/10.1021/acs.orglett.2c01890
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