Abstract
Abstract Developing catalysts comparable to natural enzymes that achieve only specific reactions has long been a key challenge in the field of molecular synthesis. Long-range olefin migration reactions have attracted great interest as molecular transformation reactions that can realize remote re-functionalization of a molecule with high atom economy. Herein we report that linear alkenyl alcohols of a certain chain length can chemically activate Pd centers precisely arranged in a porous metal-macrocycle framework (MMF), thereby promoting substrate-specific, catalytic long-range olefin migration reactions that produce aldehydes or ketones. Furthermore, MMF can be chemically activated by highly reactive alkenyl alcohol substrates, converting another olefinic substrate that normally would not react with nonactivated MMF into an olefin-migrated product at a high conversion. These reaction specificities are discussed in relation to the arrangement mode of the Pd active centers in the confined space.
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