Synthesis of gem-difluoromethylene building blocks through regioselective allylation of gem-difluorocyclopropanes.
gem-Difluorocyclopropane derivatives react with allyltributylstannane in the presence of 2,2'-azobis(isobutyronitrile) to afford 1,6-dienes with a gem-difluoromethylene moiety at the allylic position. The reaction proceeds regioselectively with high yields, and the 1,6-dinenes obtained are good precursors for cyclic systems containing a gem-difluoromethylene moiety. Although S-methyl carbonodithioate also works as a leaving group, rearrangement of the leaving group competes with the desired allylation, depending on the amount of allyltributylstannane.
Department of Chemistry and Biotechnology, Graduate School of Engineering, Tottori University , 4-101 Koyama-minami, Tottori 680-8552, Japan.
Daisuke
D
Munemori
Kent
K
Narita
Toshiki
T
Nokami
Toshiyuki
T
Itoh
D002384:Catalysis; D020650:Combinatorial Chemistry Techniques; D003521:Cyclopropanes / Q000737:chemistry*; D006845:Hydrocarbons, Fluorinated / Q000138:chemical synthesis* / Q000737:chemistry*; D015394:Molecular Structure; D009947:Organotin Compounds / Q000737:chemistry; D013237:Stereoisomerism
D003521:Cyclopropanes; D006845:Hydrocarbons, Fluorinated; D009947:Organotin Compounds