Storey, Caroline M. and Kalpokas, Audrius and Gyton, Matthew R. and Krämer, Tobias and Chaplin, Adrian B. (2020) A shape changing tandem Rh(CNC) catalyst: preparation of bicyclo[4.2.0]octa-1,5,7-trienes from terminal aryl alkynes. Chemical Science, 11 (8). pp. 2051-2057. ISSN 2041-6520

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Abstract

The preparation of a range of tetraaryl-substituted bicyclo[4.2.0]octa-1,5,7-trienes using a one-pot procedure starting from terminal aryl alkynes and catalysed by a rhodium(I) complex is reported. This synthesis proceeds by a reaction sequence involving head-to-tail homocoupling of the terminal alkyne and zipper annulation of the resulting gem-enyne. The rhodium catalyst employed is notable for the incorporation of a flexible NHC-based pincer ligand, which is suggested to interconvert between mer- and fac-coordination modes to fulfil the orthogonal mechanistic demands of the two transformations. Evidence for this interesting auto-tandem action of the catalyst is provided by reactions of the precatalyst with model substrates, corroborating proposed intermediates in both component cycles, and norbornadiene, which reversibly captures the change in pincer ligand coordination mode, along with a DFT-based computational analysis.

Item Type:	Article
Keywords:	shape changing tandem; Rh(CNC) catalyst; preparation; bicyclo[4.2.0]octa-1,5,7-trienes; terminal; aryl alkynes;
Academic Unit:	Faculty of Science and Engineering > Chemistry Faculty of Science and Engineering > Research Institutes > Hamilton Institute
Item ID:	15537
Identification Number:	https://doi.org/10.1039/c9sc06153c
Depositing User:	Tobias Kraemer
Date Deposited:	21 Feb 2022 16:39
Journal or Publication Title:	Chemical Science
Publisher:	Royal Society of Chemistry
Refereed:	Yes
URI:	Publisher
Use Licence:	This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here

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