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

摘要

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 C_1-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-l,7-dien-9-ones (Pauson—Khand-type product), 3-alkylidene-1-phenylsulfonyl-2-vinylcyclo-heptene derivatives, and bicyclo[5.2.0]nonene frameworks.