Dramatic changes in Fischer carbene reactivity occur in the presence of [Ni(cod)2]. Thus, instead of Dötz [3+2+1] benzannulation giving substituted phenols, alkenyl carbene complexes incorporate two equivalents of alkyne in a [3+2+2] cyclization, while simple chromium carbene complexes undergo a [2+2+2+1] cyclization (see scheme). These cyclizations are regio- and diastereoselective. cod=1,5-cyclooctadiene.
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Barluenga et al. (2003) studied this question.
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