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Rhodium(I)‐Catalyzed Cyclization of Allenynes with a Carbonyl Group through Unusual Insertion of a CO Bond into a Rhodacycle Intermediate
Author(s) -
Oonishi Yoshihiro,
Yokoe Takayuki,
Hosotani Akihito,
Sato Yoshihiro
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201308824
Subject(s) - rhodium , chemistry , reductive elimination , octane , catalysis , hydride , medicinal chemistry , stereochemistry , organic chemistry , metal
Rhodium(I)‐catalyzed cyclization of allenynes with a tethered carbonyl group was investigated. An unusual insertion of a CO bond into the C(sp 2 )–rhodium bond of a rhodacycle intermediate occurs via a highly strained transition state. Direct reductive elimination from the obtained rhodacyle intermediate proceeds to give a tricyclic product containing an 8‐oxabicyclo[3.2.1]octane skeleton, while β‐hydride elimination from the same intermediate gives products that contain fused five‐ and seven‐membered rings in high yields.