Arynes are highly reactive intermediates that may be used strategically in synthesis
by trapping with arynophilic reagents. However, ‘arynophilicity’ of such reagents
is almost completely anecdotal and predicting which ones will be efficient traps is
often challenging. Here, we describe a systematic study to parameterize the arynophilicity
of a wide range of reagents known to trap arynes. A relative reactivity scale, based
on one-pot competition experiments, is presented by using furan as a reference arynophile
and 3-chlorobenzyne as a the aryne. More than 15 arynophiles that react in pericyclic
reactions, nucleophilic addition, and σ-bond insertion reactions are parameterized with arynophilicity (A) values, and multiple
aryne precursors are applicable.
Key words
LFER - aryne - arynophile - percyclic reaction - δ-bond insertion - nucleophilic addition
