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Crossed McMurry Coupling Reactions for Porphycenic Macrocycles: Non‐Statistical Selectivity and Rationalisation
Author(s) -
Cowie Thomas Y.,
Kennedy Lorna,
Żurek Justyna M.,
Paterson Martin J.,
Bebbington Magnus W. P.
Publication year - 2015
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201500221
Subject(s) - annulene , chemistry , selectivity , density functional theory , computational chemistry , photochemistry , coupling reaction , coupling (piping) , organic chemistry , catalysis , materials science , metallurgy
Abstract Crossed McMurry reactions of bifuran‐ or bithiophenedicarbaldehydes with bipyrroledicarbaldehydes have been studied for the first time. Only those porphycenic macrocycles derived from homocoupled McMurry products were formed. The results are explained by using both density functional theory and electron propagator computations to model the electron affinity of the dialdehyde starting materials. It was predicted that bifuran\bithiophene cross‐coupling would indeed occur, and this was demonstrated by the first synthesis of a novel dioxa,dithio hetero‐porphycenoid annulene. This approach will allow the prior identification of viable substrates for related crossed McMurry reactions.