Divergent Construction of Polycyclic Frameworks Enabled by Sequential Ru-Catalyzed [2 + 2 + 2] Cycloaddition of
Yoshihiko Yamamoto1, Yutaro Hayashi1, Kenichi Yoshimura1
1Department of Basic Medicinal Sciences, Graduate School of Pharmaceutical Sciences, Nagoya University, Chikusa, Nagoya 464-8601, Japan.
Abstract:
The Ru-catalyzed [2 + 2 + 2] cycloaddition of iododiynes with ex situ generated acetylene gas afforded bicyclic iodobenzenes in high yields. The obtained bicyclic iodobenzenes were subsequently subjected to Pd/NBE-mediated Catellani-type annulations, yielding a variety of polycyclic products. Control experiments using a deuterated bicyclic iodobenzene, which was prepared using acetylene-d2 ex situ generated from CaC2 and D2O, revealed that the C-H activation step leading to a palladacycle intermediate is rate-determining when ethyl (E)-6-bromohex-2-enoate was used as a reaction partner.
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