Highly Diastereoselective Preparation of Tertiary Alkyl Isonitriles by Stereoinvertive Nucleophilic Substitution at a Nonclassical Carbocation

[Image: see text] A highly efficient SnCl(4)-catalyzed nucleophilic isocyanation of cyclopropyl ethers has been developed. The reaction proceeds at the quaternary carbon stereocenter of the cyclopropane with a complete inversion of configuration, providing a new avenue for the construction of synthe...

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Autores principales: Chen, Xu, Marek, Ilan
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10088034/
https://www.ncbi.nlm.nih.gov/pubmed/36976777
http://dx.doi.org/10.1021/acs.orglett.3c00583
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author Chen, Xu
Marek, Ilan
author_facet Chen, Xu
Marek, Ilan
author_sort Chen, Xu
collection PubMed
description [Image: see text] A highly efficient SnCl(4)-catalyzed nucleophilic isocyanation of cyclopropyl ethers has been developed. The reaction proceeds at the quaternary carbon stereocenter of the cyclopropane with a complete inversion of configuration, providing a new avenue for the construction of synthetically challenging tertiary alkyl isonitriles with high diastereopurity. The diversity of the incorporated isocyanide group has been demonstrated by the transformation of tertiary alkyl isonitriles into the corresponding tertiary alkyl amines, amides, and cyclic ketoimines.
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spelling pubmed-100880342023-04-12 Highly Diastereoselective Preparation of Tertiary Alkyl Isonitriles by Stereoinvertive Nucleophilic Substitution at a Nonclassical Carbocation Chen, Xu Marek, Ilan Org Lett [Image: see text] A highly efficient SnCl(4)-catalyzed nucleophilic isocyanation of cyclopropyl ethers has been developed. The reaction proceeds at the quaternary carbon stereocenter of the cyclopropane with a complete inversion of configuration, providing a new avenue for the construction of synthetically challenging tertiary alkyl isonitriles with high diastereopurity. The diversity of the incorporated isocyanide group has been demonstrated by the transformation of tertiary alkyl isonitriles into the corresponding tertiary alkyl amines, amides, and cyclic ketoimines. American Chemical Society 2023-03-28 /pmc/articles/PMC10088034/ /pubmed/36976777 http://dx.doi.org/10.1021/acs.orglett.3c00583 Text en © 2023 The Authors. Published by 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 Chen, Xu
Marek, Ilan
Highly Diastereoselective Preparation of Tertiary Alkyl Isonitriles by Stereoinvertive Nucleophilic Substitution at a Nonclassical Carbocation
title Highly Diastereoselective Preparation of Tertiary Alkyl Isonitriles by Stereoinvertive Nucleophilic Substitution at a Nonclassical Carbocation
title_full Highly Diastereoselective Preparation of Tertiary Alkyl Isonitriles by Stereoinvertive Nucleophilic Substitution at a Nonclassical Carbocation
title_fullStr Highly Diastereoselective Preparation of Tertiary Alkyl Isonitriles by Stereoinvertive Nucleophilic Substitution at a Nonclassical Carbocation
title_full_unstemmed Highly Diastereoselective Preparation of Tertiary Alkyl Isonitriles by Stereoinvertive Nucleophilic Substitution at a Nonclassical Carbocation
title_short Highly Diastereoselective Preparation of Tertiary Alkyl Isonitriles by Stereoinvertive Nucleophilic Substitution at a Nonclassical Carbocation
title_sort highly diastereoselective preparation of tertiary alkyl isonitriles by stereoinvertive nucleophilic substitution at a nonclassical carbocation
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10088034/
https://www.ncbi.nlm.nih.gov/pubmed/36976777
http://dx.doi.org/10.1021/acs.orglett.3c00583
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AT marekilan highlydiastereoselectivepreparationoftertiaryalkylisonitrilesbystereoinvertivenucleophilicsubstitutionatanonclassicalcarbocation

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