Terminal alkyne coupling reactions through a ring: effect of ring size on rate and regioselectivity

Chemistry : a European Journal
Caroline M StoreyAdrian B Chaplin

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 studi...Continue Reading

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Citations

Nov 12, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Thomas M Hood, Adrian B Chaplin
Jan 30, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Thomas M Hood, Adrian B Chaplin
Apr 4, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Ronja Jordan, Doris Kunz

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