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Terminal alkyne coupling reactions through a ring : effect of ring size on rate and regioselectivity
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Storey, Caroline M., Gyton, Matthew R., Andrew, Rhiann E. and Chaplin, Adrian B. (2020) Terminal alkyne coupling reactions through a ring : effect of ring size on rate and regioselectivity. Chemistry - A European Journal, 26 (64). pp. 14715-14723. doi:10.1002/chem.202002962 ISSN 0947-6539.
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WRAP-terminal-alkyne-coupling-reactions-through-a-ring-effect-ring-size-rate-regioselectivity-Chaplin-2020.pdf - Accepted Version Embargoed item. Restricted access to Repository staff only - Requires a PDF viewer. Download (5Mb) |
Official URL: https://doi.org/10.1002/chem.202002962
Abstract
Terminal alkyne coupling reactions promoted by rhodium(I) complexes of macrocyclic NHC‐based pincer ligands – which feature dodecamethylene, tetradecamethylene or hexadecamethylene wingtip linkers viz. [Rh(CNC‐n)(C2H4)][BArF4] (n = 12, 14, 16; ArF = 3,5‐(CF3)2C6H3) – have been investigated, using the bulky alkynes HC≡CtBu and HC≡CAr′ (Ar′ = 3,5‐tBu2C6H3) as substrates. These stoichiometric reactions proceed with formation of rhodium(III) alkynyl alkenyl derivatives and produce rhodium(I) complexes of conjugated 1,3‐enynes by C–C bond reductive elimination through the annulus of the ancillary ligand. The intermediates are formed with orthogonal regioselectivity, with E‐alkenyl complexes derived from HC≡CtBu and gem‐alkenyl complexes derived from HC≡CAr′, and the reductive elimination step is appreciably affected by the ring size of the macrocycle. For the homocoupling of HC≡CtBu, E‐tBuC≡CCH=CHtBu is produced via direct reductive elimination from the corresponding rhodium(III) alkynyl E‐alkenyl derivatives with increasing efficacy as the ring is expanded. In contrast, direct reductive elimination of Ar′C≡CC(=CH2)Ar′ is encumbered relative to head‐to‐head coupling of HC≡CAr′ and it is only with the largest macrocyclic ligand studied that the two processes are competitive. These results showcase how macrocyclic ligands can be used to interrogate the mechanism and tune the outcome of terminal alkyne coupling reactions, and are discussed with reference to catalytic reactions mediated by the acyclic homologue [Rh(CNC‐Me)(C2H4)][BArF4] and solvent effects.
Item Type: | Journal Article | ||||||||||||
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Subjects: | Q Science > QD Chemistry | ||||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||||||
Library of Congress Subject Headings (LCSH): | Organometallic compounds -- Synthesis, Chemical reactions, Chemistry, Organic, Organometallic compounds -- Reactivity | ||||||||||||
Journal or Publication Title: | Chemistry - A European Journal | ||||||||||||
Publisher: | Wiley - V C H Verlag GmbH & Co. KGaA | ||||||||||||
ISSN: | 0947-6539 | ||||||||||||
Official Date: | 17 November 2020 | ||||||||||||
Dates: |
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Volume: | 26 | ||||||||||||
Number: | 64 | ||||||||||||
Page Range: | pp. 14715-14723 | ||||||||||||
DOI: | 10.1002/chem.202002962 | ||||||||||||
Status: | Peer Reviewed | ||||||||||||
Publication Status: | Published | ||||||||||||
Reuse Statement (publisher, data, author rights): | This is the peer reviewed version of the following article: Storey, C..M., Gyton, M..R., Andrew, R..E. and Chaplin, A..B. (2020), Terminal alkyne coupling reactions through a ring: effect of ring size on rate and regioselectivity. Chem. Eur. J.. Accepted Author Manuscript. doi:10.1002/chem.202002962, which has been published in final form at https://doi.org/10.1002/chem.202002962. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. | ||||||||||||
Access rights to Published version: | Open Access (Creative Commons) | ||||||||||||
Date of first compliant deposit: | 22 July 2020 | ||||||||||||
Date of first compliant Open Access: | 16 December 2020 | ||||||||||||
RIOXX Funder/Project Grant: |
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