TY - JOUR A1 - Konno, Tsutomu A1 - Kishi, Misato A1 - Ishihara, Takashi T1 - Highly stereocontrolled synthesis of trans-enediynes via carbocupration of fluoroalkylated diynes JF - Beilstein Journal of Organic Chemistry PY - 2012/// VL - 8 SP - 2207 EP - 2213 SN - 1860-5397 DO - 10.3762/bjoc.8.249 PB - Beilstein-Institut JA - Beilstein J. Org. Chem. UR - https://doi.org/10.3762/bjoc.8.249 KW - carbocupration KW - carbometallation KW - diyne KW - enediyne KW - fluorine KW - highly regioselective KW - highly stereoselective N2 - Treatment of readily prepared (Z)-6-benzyloxy-1,1,1,2-tetrafluoro-6-methyl-2-hepten-4-yne with 1.5 equiv of LHMDS in −78 °C for 1 h gave the corresponding trifluoromethylated diyne in an excellent yield. This diyne was found to be a good substrate for the carbocupration with various higher-ordered cyanocuprates to give the corresponding vinylcuprates in a highly regio- and stereoselective manner. The in situ generated vinylcuprates could react very smoothly with an excess amount of iodine, the vinyl iodides being obtained in high yields. Thus-obtained iodides underwent a very smooth Sonogashira cross-coupling reaction to afford various trans-enediynes in high yields. ER -