CC BY 4.0 · Synthesis 2023; 55(09): 1355-1366
DOI: 10.1055/a-2008-9505
special topic
Bürgenstock Special Section 2022 – Future Stars in Organic Chemistry

Exploring Silyl Protecting Groups for the Synthesis of Carbon Nanohoops

Remigiusz B. Kręcijasz
a   Van't Hoff Institute for Molecular Sciences, University of Amsterdam, PO Box 94157, 1090 GD Amsterdam, Netherlands
,
Juraj Malinčík
b   Department of Chemistry, Biochemistry and Pharmaceutical Sciences, University of Bern, Freiestrasse 3, 3012 Bern, Switzerland
c   Prievidza Chemical Society, M. Hodžu 10/16, 971 01 Prievidza, Slovakia
,
Tomáš Šolomek  ∗
a   Van't Hoff Institute for Molecular Sciences, University of Amsterdam, PO Box 94157, 1090 GD Amsterdam, Netherlands
c   Prievidza Chemical Society, M. Hodžu 10/16, 971 01 Prievidza, Slovakia
› Author AffiliationsThis project received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (Grant No. 949397).
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Abstract

The synthesis of topological molecular nanocarbons, such as hoop-like [n]cycloparaphenylenes, requires the use of spatially prearranged, pro-aromatic units to overcome a build-up of large molecular strain in their curved structures. The used cyclohexadienyl units, however, contain tertiary alcohols that need protection to prevent side reactions until the aromatization step that affords the final curved hydrocarbon. Although alkyl and triethylsilyl groups have been successfully applied as protecting groups for this purpose, each suffers from specific drawbacks. Here, we explore the potential of sterically more crowded silyl groups, namely, tert-butyldimethylsilyl and triisopropylsilyl, as alternatives to the established protection strategies. We show that tert-butyldimethylsilyl can be easily installed and removed under mild conditions, displaying markedly higher resistance towards acids or bases than the triethylsilyl group used to date. Unlike in the case of alkyl groups, tert-butyldimethylsilyl also preserves a high stereoselectivity during the nucleophilic additions of ArLi. Furthermore, we demonstrate that both tert-butyldimethylsilyl and triethylsilyl groups can be installed on the same substrate, and that the latter be selectively deprotected. Thus, the high stereoselectivity, improved stability, and easy deprotection make tert-butyldimethylsilyl an excellent protecting group for the synthesis of carbon nanohoops.

Key words

topological molecular nanocarbons - carbon nanohoops - cycloparaphenylenes - protecting groups - silyl ethers - tert-butyldimethylsilyl - macrocycles - orthogonality

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2008-9505.
  • Supporting Information


Publication History

Received: 01 November 2022

Accepted after revision: 06 January 2023

Accepted Manuscript online:
06 January 2023

Article published online:
09 February 2023

© 2023. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by/4.0/)

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