American Chemical Society
jo050770z_si_002.pdf (7.51 MB)

Rh(I)-Catalyzed Pauson−Khand Reaction and Cycloisomerization of Allenynes:  Selective Preparation of Monocyclic, Bicyclo[m.3.0], and Bicyclo[5.2.0] Ring Systems

Download (7.51 MB)
journal contribution
posted on 2005-09-02, 00:00 authored by Chisato Mukai, Fuyuhiko Inagaki, Tatsunori Yoshida, Katsuya Yoshitani, Yasuyuki Hara, Shinji Kitagaki
Rhodium(I)-catalyzed PKR of allenynes was found to be applicable for constructing azabicyclo[5.3.0]decadienone as well as oxabicyclo[5.3.0]decadienone frameworks. In addition, a reliable procedure for constructing a 10-monosubstituted bicyclo[5.3.0]deca-1,7-dien-9-one ring system by the rhodium(I)-catalyzed PKR of allenynes was developed under the condition of 10 atm of CO. Investigation of the rhodium(I)-catalyzed cycloisomerization of 4-phenylsulfonylnona-2,3-dien-8-ynes under nitrogen atmosphere gave the corresponding cyclohexene derivatives, whereas the C1-homologated allenynes produced cycloheptene derivatives and/or bicyclo[5.2.0]nonene skeletons depending on the substitution pattern at the allenic terminus. Thus, proper choice of the starting allenynes and reaction conditions led to the selective formation of 2-phenylsulfonylbicyclo[5.3.0]deca-1,7-dien-9-ones (Pauson−Khand-type product), 3-alkylidene-1-phenylsulfonyl-2-vinylcycloheptene derivatives, and bicyclo[5.2.0]nonene frameworks.