W(CO)5(L)-catalyzed tandem intramolecular cyclopropanation/cope rearrangement for the stereoselective construction of bicyclo[5.3.0]decane framework.
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)5(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)6 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)5(L)-catalyzed electrophilic activation of alkynes, occurs to give synthetically useful functionalized bicyclo[5.3.0]decane derivatives stereoselectively.
Kusama
Hiroyuki
H
Department of Chemistry, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8551, Japan.
Onizawa
Yuji
Y
Iwasawa
Nobuharu
N
D000480:Alkynes / Q000737:chemistry*; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D001952:Bridged-Ring Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D003521:Cyclopropanes / Q000737:chemistry*; D005663:Furans / Q000737:chemistry; D008024:Ligands; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D012833:Siloxanes / Q000737:chemistry*; D013237:Stereoisomerism; D017973:Tungsten Compounds / Q000737:chemistry*
C516926:3-siloxy-1,3,9-trien-7-yne; D000480:Alkynes; D001643:Bridged Bicyclo Compounds; D001952:Bridged-Ring Compounds; D003521:Cyclopropanes; D005663:Furans; D008024:Ligands; D009942:Organometallic Compounds; D012833:Siloxanes; D017973:Tungsten Compounds; C516925:bicyclo(5.3.0)decane