Storey, Caroline M., Kalpokas, Audrius, Gyton, Matthew R., 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. doi:10.1039/C9SC06153C ISSN 2041-6520.

Preview

PDF WRAP-shape-changing-tandem-Rh(CNC)-catalyst-final-Chaplin-2020.pdf - Published Version - Requires a PDF viewer. Available under License Creative Commons Attribution. Download (1476Kb) | Preview

Request Changes to record.

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:	Journal Article
Subjects:	Q Science > QD Chemistry
Divisions:	Faculty of Science, Engineering and Medicine > Science > Chemistry
Library of Congress Subject Headings (LCSH):	Alkynes, Catalysis, Ligand binding (Biochemistry)
Journal or Publication Title:	Chemical Science
Publisher:	Royal Society of Chemistry
ISSN:	2041-6520
Official Date:	22 January 2020
Dates:	Date Event 22 January 2020 Available 21 January 2020 Accepted
Volume:	11
Number:	8
Page Range:	pp. 2051-2057
DOI:	10.1039/C9SC06153C
Status:	Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Open Access (Creative Commons)
Date of first compliant deposit:	24 January 2020
Date of first compliant Open Access:	5 February 2020
RIOXX Funder/Project Grant:	Project/Grant ID RIOXX Funder Name Funder ID 637313 European Research Council http://dx.doi.org/10.13039/501100000781 UNSPECIFIED National University of Ireland, Maynooth http://dx.doi.org/10.13039/501100001633 UF100592, UF150675, A.B.C Royal Society http://dx.doi.org/10.13039/501100000288

Request changes or add full text files to a record

Repository staff actions (login required)

View Item

Downloads