1600522-25-5Relevant academic research and scientific papers
Rhodium(I)-catalyzed cyclization of allenynes with a carbonyl group through unusual insertion of a C=O bond into a rhodacycle intermediate
Oonishi, Yoshihiro,Yokoe, Takayuki,Hosotani, Akihito,Sato, Yoshihiro
supporting information, p. 1135 - 1139 (2014/03/21)
Rhodium(I)-catalyzed cyclization of allenynes with a tethered carbonyl group was investigated. An unusual insertion of a C=O 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. Unusual insertion: During the title reaction, a C=O bond is inserted into the C(sp2)-Rh bond of rhodacycle intermediate I. The insertion occurs via a highly strained transition state. Direct reductive elimination from II gives a tricyclic product containing an 8-oxabicyclo[3.2.1] octane skeleton, whereas β-hydride elimination from II gives products with fused five- and seven-membered rings. Copyright
