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Asymmetric Catalysis in Chiral Solvents: Chirality Transfer with Amplification of Homochirality through a Helical Macromolecular Scaffold

[Image: see text] Use of chiral solvents in asymmetric synthesis as a sole source of enantioselection remains largely unexplored in organic synthesis. We found that the use of a helical macromolecular catalyst of which helical chirality is dynamically formed in chiral solvents allowed several mechan...

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Autores principales: Nagata, Yuuya, Takeda, Ryohei, Suginome, Michinori
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2019
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6661863/
https://www.ncbi.nlm.nih.gov/pubmed/31404214
http://dx.doi.org/10.1021/acscentsci.9b00330
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author Nagata, Yuuya
Takeda, Ryohei
Suginome, Michinori
author_facet Nagata, Yuuya
Takeda, Ryohei
Suginome, Michinori
author_sort Nagata, Yuuya
collection PubMed
description [Image: see text] Use of chiral solvents in asymmetric synthesis as a sole source of enantioselection remains largely unexplored in organic synthesis. We found that the use of a helical macromolecular catalyst of which helical chirality is dynamically formed in chiral solvents allowed several mechanistically different reactions to proceed with high enantioselectivity. In this system, the chirality of the solvent, such as limonene, induces a configurational imbalance to the helical macromolecular scaffold of the catalyst, and in turn to the reaction products through palladium-catalyzed asymmetric reactions including Suzuki-Miyaura cross-coupling (up to 98% ee), styrene hydrosilylation (up to 95% ee), and silaboration (up to 89% ee). Not only enantiomerically pure limonene but also limonene with low enantiomeric excesses induce single-handed helical structures with majority-rule-based amplification of homochirality. The helical conformation of the macromolecular catalyst was retained even in the absence of limonene in the solid state, enabling asymmetric cross-coupling in achiral solvent with high enantioselectivity.
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spelling pubmed-66618632019-08-09 Asymmetric Catalysis in Chiral Solvents: Chirality Transfer with Amplification of Homochirality through a Helical Macromolecular Scaffold Nagata, Yuuya Takeda, Ryohei Suginome, Michinori ACS Cent Sci [Image: see text] Use of chiral solvents in asymmetric synthesis as a sole source of enantioselection remains largely unexplored in organic synthesis. We found that the use of a helical macromolecular catalyst of which helical chirality is dynamically formed in chiral solvents allowed several mechanistically different reactions to proceed with high enantioselectivity. In this system, the chirality of the solvent, such as limonene, induces a configurational imbalance to the helical macromolecular scaffold of the catalyst, and in turn to the reaction products through palladium-catalyzed asymmetric reactions including Suzuki-Miyaura cross-coupling (up to 98% ee), styrene hydrosilylation (up to 95% ee), and silaboration (up to 89% ee). Not only enantiomerically pure limonene but also limonene with low enantiomeric excesses induce single-handed helical structures with majority-rule-based amplification of homochirality. The helical conformation of the macromolecular catalyst was retained even in the absence of limonene in the solid state, enabling asymmetric cross-coupling in achiral solvent with high enantioselectivity. American Chemical Society 2019-07-03 2019-07-24 /pmc/articles/PMC6661863/ /pubmed/31404214 http://dx.doi.org/10.1021/acscentsci.9b00330 Text en Copyright © 2019 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Nagata, Yuuya
Takeda, Ryohei
Suginome, Michinori
Asymmetric Catalysis in Chiral Solvents: Chirality Transfer with Amplification of Homochirality through a Helical Macromolecular Scaffold
title Asymmetric Catalysis in Chiral Solvents: Chirality Transfer with Amplification of Homochirality through a Helical Macromolecular Scaffold
title_full Asymmetric Catalysis in Chiral Solvents: Chirality Transfer with Amplification of Homochirality through a Helical Macromolecular Scaffold
title_fullStr Asymmetric Catalysis in Chiral Solvents: Chirality Transfer with Amplification of Homochirality through a Helical Macromolecular Scaffold
title_full_unstemmed Asymmetric Catalysis in Chiral Solvents: Chirality Transfer with Amplification of Homochirality through a Helical Macromolecular Scaffold
title_short Asymmetric Catalysis in Chiral Solvents: Chirality Transfer with Amplification of Homochirality through a Helical Macromolecular Scaffold
title_sort asymmetric catalysis in chiral solvents: chirality transfer with amplification of homochirality through a helical macromolecular scaffold
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6661863/
https://www.ncbi.nlm.nih.gov/pubmed/31404214
http://dx.doi.org/10.1021/acscentsci.9b00330
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AT suginomemichinori asymmetriccatalysisinchiralsolventschiralitytransferwithamplificationofhomochiralitythroughahelicalmacromolecularscaffold