Abstract
Arynes and donor–acceptor (D–A) cyclopropanes are two classes of strained systems having the potential for numerous applications in organic synthesis. The last two decades have witnessed a renaissance of interest in the chemistry of these species primarily because of the mild and robust methods for their generation or activation. Commonly, arynes as easily polarizable systems result in 1,2‐disubstitution, whereas D‐A cyclopropanes as polarized systems lead to 1,3‐bisfunctionalization thereby showing striking similarities. Transformations with 1,2‐ and 1,3‐dipoles afford cyclic structures. With arynes, emerging four‐membered rings as intermediates might react further, whereas the analogous five‐membered rings obtained from D–A cyclopropanes are most often the final products. However, there are a few cases where these intermediates behave surprisingly differently. This Minireview highlights the parallels in reactivity between arynes and D–A cyclopropanes thereby shedding light on the neglected similarities of these two reactive species.
Highlights
Arynes and donor–acceptor (D–A) cyclopropanes are two classes of review is to highlight the similarities in strained systems having the potential for numerous applications in organic synthesis
Were postulated as an intermediate in arynes as polarizable systems result in 1,2-disubstitution, whereas D-A cyclopropanes as polarized systems lead to 1,3bisfunctionalization thereby showing striking similarities
The Stoltz and Yoshida groups independently reported that arynes react with b-ketoesters or 1,3dicarbonyls 13 to give the acyl-alkylation product resulting from a CÀC bond cleavage of the activated dicarbonyl compound followed by insertion (Scheme 4).[22]
Summary
The Stoltz and Yoshida groups independently reported that arynes react with b-ketoesters or 1,3dicarbonyls 13 to give the acyl-alkylation product resulting from a CÀC bond cleavage of the activated dicarbonyl compound followed by insertion (Scheme 4).[22] Mechanistically, one assumes an initial nucleophilic attack of the enolate on the triple bond of the aryne, ring-closure to a fourmembered ring, and fragmentation to the 1,2-disubstituted benzene derivative Such a cleavage of an enol CÀC bond has never been observed so far in the reaction with D–A cyclopropanes.
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