Synthesis of new fluorovinylzinc reagents and their application for synthesis of fluorine analogs of protoporphyrin

Treatment of chlorotrifluoroethene (4) or 2-chloro-1,1-difluoroethene (5) with sec-butyllithium in the presence of zinc chloride gave new fluorovinyl zinc reagents (12 or 13). These were distinguished by 19F NMR from trifluorovinylzinc chloride (7) or 1-chloro-2,2-difluorovinylzinc chloride (8) obtained by Normant’s group, via preliminary formation of fluorinated vinyllithium reagents by treatment of 4 or 5 with sec-butyllithium followed by addition of zinc chloride. Reaction of 12 or 13 with 3,8-diiododeuteroporphyrin dimethyl ester (9) in the presence of a palladium catalyst produced 3,8-bis(trifluorovinyl) or 3,8-bis(1-chloro-2,2-difluorovinyl)deuteroporphyrin dimethyl ester (10 or 11) quantitatively, while the same reaction of metal complex of 9 with the reagents (7 or 8) formed by Normant’s method gave 10 or 11 in the yields of 23 or 56%, respectively.