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Chain Walking as a Strategy for Carbon–Carbon Bond Formation at Unreactive Sites in Organic Synthesis: Catalytic Cycloisomerization of Various 1,n-Dienes

Author:
Hamasaki, Taro, Aoyama, Yuka, Kawasaki, Junichi, Kakiuchi, Fumitoshi, Kochi, Takuya
Source:
Journal of the American Chemical Society 2015 v.137 no.51 pp. 16163-16171
ISSN:
1520-5126
Subject:
alkenes, carbon, catalysts, chemical bonding, chromatography, hydrogenation, nitrogen, palladium, silica gel, silver nitrate
Abstract:
Carbon–carbon bond formation at unreactive sp³-carbons in small organic molecules via chain walking was achieved for the palladium-catalyzed cycloisomerization of 1,n-dienes. Various 1,n-dienes (n = 7–14) such as those containing cyclic alkenes, acyclic internal alkenes, and a trisubstituted alkene can be used for the chain-walking cycloisomerization/hydrogenation process, and five-membered ring compounds including simple cyclopentane and pyrrolidine derivatives can easily be prepared. Chain walking over a tertiary carbon was also found to be possible in the cycloisomerization. It is not necessary for the linker portion of the diene to contain a quaternary center, and diene substrates with two alkene moieties linked by a tertiary carbon or a nitrogen atom can also be used as substrates. Column chromatography using silica gel containing silver nitrate was found to be effective for isolating some of the cycloisomerization products without hydrogenation. Deuterium-labeling experiments provided direct evidence to show that the reaction proceeds via a chain-walking mechanism.
Agid:
5416923