%0 Journal Article
%T Highly stereocontrolled synthesis of trans-enediynes via carbocupration of fluoroalkylated diynes
%A Tsutomu Konno
%A Misato Kishi
%A Takashi Ishihara
%J Beilstein Journal of Organic Chemistry
%D 2012
%I 
%R 10.3762/bjoc.8.249
%X 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 ˇăC 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.
%K carbocupration
%K carbometallation
%K diyne
%K enediyne
%K fluorine
%K highly regioselective
%K highly stereoselective
%U http://dx.doi.org/10.3762/bjoc.8.249