W(CO)<sub>5</sub>(L)-Catalyzed Tandem Intramolecular Cyclopropanation/Cope Rearrangement for the Stereoselective Construction of Bicyclo[5.3.0]decane Framework Hiroyuki Kusama Yuji Onizawa Nobuharu Iwasawa 10.1021/ja0671924.s004 https://acs.figshare.com/articles/dataset/W_CO_sub_5_sub_L_Catalyzed_Tandem_Intramolecular_Cyclopropanation_Cope_Rearrangement_for_the_Stereoselective_Construction_of_Bicyclo_5_3_0_decane_Framework/3038557 Utilizing the biscarbene character of electrophilically activated alkynes, a novel tandem intramolecular cyclopropanation/Cope rearrangement of 3-siloxy-1,3,9-trien-7-ynes catalyzed by W(CO)<sub>5</sub>(L) for the stereoselective construction of bicyclo[5.3.0]decane framework is achieved. When 3-siloxy-1,3,9-trien-7-ynes were treated with a catalytic amount of W(CO)<sub>6</sub> under photoirradiation, bicyclo[5.3.0]decanes were obtained in good yield stereoselectively. In this reaction, the Cope rearrangement of the divinylcyclopropane intermediates, generated by the intramolecular cyclopropanation of 3-siloxy-1,3,9-trien-7-ynes based on the W(CO)<sub>5</sub>(L)-catalyzed electrophilic activation of alkynes, occurs to give synthetically useful functionalized bicyclo[5.3.0]decane derivatives stereoselectively. 2006-12-27 00:00:00 bicyclo stereoselectively Cope rearrangement biscarbene character divinylcyclopropane intermediates siloxy intramolecular cyclopropanation stereoselective construction Stereoselective Construction alkyne