| This thesis includes these scientific achievements: 1-Bromo-1-fluoroalkenes (E/Z ≈ 1:1) can isomerize to high E/Z ratios (E/Z > 75:25) when they are stored at -20°C (for 1-bromo-1-fluorostyrenes) or alternatively by photolysis at 254 nm, and can be kinetically reduced to obtain (Z)-1-bromo-1-fluoroalkenes (E/Z = 0:100).;High E/Z ratio 1-bromo-1-fluoroalkenes can undergo palladium-catalyzed carboalkoxylation to get high Z/E alpha-fluoro-alpha,beta-unsaturated esters (Z/E ≥ 98:2), or carboamidation to give pure (Z)-alpha-fluoro-alpha,beta-unsaturated amides. (Z)-1-bromo-1-fluoroalkenes can undergo similar carboalkoxylation to give pure (E)-alpha-fluoro-alpha,beta-unsaturated esters, or carboamidation to get pure (E)-alpha-fluoro-alpha,beta-unsaturated amides.;High E/Z 1-bromo-1-fluoroalkenes can undergo Stille coupling reaction with aryl stannanes to afford pure (Z)-alpha-fluorostilbenes. The Suzuki coupling reactions between (Z)-1-bromo-1-fluoroalkenes and aryl boronic acids lead to (E)-alpha-fluorostilbenes or (E)-1-fluoroalkenes.;High E/Z 1-bromo-1-fluoroalkenes can react with Pd(PPh3) 4 and Bu3SnSnBu3 to successfully give symmetrical dienes (1Z, 3Z)-RCH=CFCF=CHR. Similar symmetrical dienes (1E, 3E)-RCH=CFCF=CHR were also prepared.;(2E, 4Z)-4-Fluorodienonates were successfully prepared via the Heck reaction from high E/Z 1-bromo-1-fluoroalkenes.;When (E)-monofluoroenynes reacted with DABCO in NMP at reflux temperature, 3-fluoro-1-substituted naphthalenes were successfully prepared. A mechanism is proposed; the limitation and scope of this reaction was studied. |
