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Treatment of β-fluoroalkylated-α,β-unsaturated ketones with 1.2 equiv. of various arylboronic acids in the presence of 5 mol% of [Rh(COD)(2)]BF(4) and 6 mol% of (S)-BINAP in toluene/H(2)O (v/v = 4/1) at the reflux temperature for 3 h gave the corresponding Michael adducts in high yields with over 90% enantioselectivity. Though other electron-deficient alkenes, such as vinylsulfone and vinylphosphonate, were found to be much less reactive in the rhodium-catalyzed conjugate addition with arylboronic acids, the reaction of various arylstannanes toward such electron-deficient alkenes took place very smoothly to afford the corresponding adducts in high yields.

A catalytic amount of Pd(OAc)2 was successfully applied for the generation of enamines from various tertiary amines under oxidative conditions. As a synthetic application, the generated enamines were used for 1,4‐conjugate addition reactions with fluoroalkylated olefins. Thus, a catalytic amount of Pd(OAc)2 was added to a mixture of tertiary amines and fluoroalkylated olefins in N,N,‐dimethylacetamide in air, and the corresponding 1,4‐adducts were obtained in moderate to good yields for a variety of substrates. This unique reaction can allow readily available tertiary amines to be used as nucleophilic C2 synthons and is an alternative synthetic protocol for the hydroformylmethylation of olefins.

On treatment of various fluorinated internal alkynes with 1.2 equiv of hexabutylditin under the influence of 2.5 mol % of Pd(t-BuNC)(2)Cl(2) in THF at room temperature for 4 h, the bisstannylation proceeded smoothly to afford the corresponding bisstannylated cis-adducts in high yields. Thus obtained adducts were subjected to the Stille cross-coupling reaction to give the corresponding tetrasubstituted fluorine-containing alkenes with defined stereochemistry in good yields.