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]BF4 and 6 mol% of (S)-BINAP in toluene/H2O (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.

Reaction of α,β,γ,γ,γ-pentafluorocrotonates with organocuprates derived from organomagnesium or zinc reagents in THF at −78 °C for 1 h took place smoothly to generate β-metallated intermediate, of which hydrolysis gave the β-reduction product in good yield. The fluorinated vinylcopper intermediate formed by fluorine–copper exchange was found to be stable at low temperature due to the strong electron-withdrawing effect of a CF3 group, and was readily converted to various types of β-substituted products in good yields with high stereoselectivity by treating with electrophiles, such as iodine and allylic bromides.Graphical abstract. Fluorine–copper exchange reaction effectively occurred when α,β,γ,γ,γ-pentafluorocrotonates were treated with Grignard reagents or dialkylzinc in the presence of CuCN or the LiCl-complex, giving rise to β-metallated α,γ,γ,γ-tetrafluorocrotonates as an intermediate, which were converted to β-substituted α,γ,γ,γ-tetrafluorocrotonates in good yields.Highlights► Addition–elimination reaction with organocuprates furnished vinylcopper species. ► The in situ generated vinylcopper species was stable at −78 °C. ► The vinylcopper species reacted with various electrophiles. ► Fluorine-containing tetra-substituted alkenes were obtained in a single operation.

Novel and short synthetic approaches to 2,3-dideoxy-2,2,3,3-tetrafluoropyranoses or azapyranoses have been developed successfully using commercially available reagents, such as 4-bromo-3,3,4,4-tetrafluoro-1-butene. This synthetic strategy involves an intermolecular reductive coupling of 4-bromo-3,3,4,4-tetrafluoro-1-butene and various chiral aldehydes using LiBr-free MeLi as a key transformation.Graphical abstractTetrafluoroethylenated sugar derivatives could be synthesized as an optically pure form in high total yields.Highlights► Short syntheses of tetrafluoroethylenated sugar derivatives could be realized. ► The syntheses involve the intermolecular reductive coupling of CH2CHCF2CF2Br and aldehydes. ► Four types of chiral sugar derivatives could be synthesized. ► Two types of chiral azasugar derivatives could be synthesized.

Treatment of γ-fluoroallylic phosphate with various lower-ordered cyanocuprates derived from Grignard reagents, organolithium, and organozincs gave the corresponding SN2′ products having a fluorine atom at a quaternary carbon center in excellent yields. This system could be successfully extended to the chiral version, enantiomerically pure fluorine-containing materials also being obtained in high yield.

Oxidation of various fluoroalkyl-substituted methanol derivatives under the influence of a catalytic amount of sodium 2-iodobenzenesulfonate and Oxone® in CH3CN or CH3NO2 was investigated in detail. The efficiency of the newly developed oxidation was also evaluated by comparison to other oxidations, such as Dess–Martin, PDC, and Swern oxidation.Graphical abstractThe hypervalent iodine(V)-catalyzed oxidation of fluorinated alcohols to the corresponding ketones was developed as the alternative to Dess–Martin oxidation.Highlights► The hypervalent iodine(V)-catalyzed oxidation for fluorinated alcohols was established. ► Various fluorinated alcohols can be converted into the corresponding ketones in high yields. ► This system is superior to PDC, Swern oxidations, and comparable to Dess–Martin oxidation.

Intermolecular Pauson–Khand reaction of fluoroalkylated alkynes with 2-norbornene or 2,5-norbornadiene at the reflux temperature of dichloroethane proceeded smoothly to give the corresponding cyclopentenone derivatives in high yields as a mixture of regioisomers. On the other hand, intramolecular Pauson–Khand reaction of fluorine-containing 1,6-enyne proceeded in the presence of NMO or TMANO to give the bicyclic adducts in good yields. Additionally, allyl CF3-propargyl ether also underwent a smooth Pauson–Khand reaction in the presence of amine oxide, the corresponding bicyclic compounds being obtained in a highly diastereoselective manner.Graphical abstractThe intermolecular and intramolecular Pauson–Khand reaction of fluorine-containing alkynes gave the corresponding fluoroalkylated cyclopentenone derivatives in good to high yields.Highlights► Intermolecular PKR was done by using fluoroalkylated alkynes with 2-norbornene. ► Reaction at the reflux gave the cyclopentenones as a diastereomeric mixture. ► Intramolecular PKR was carried out by using teminal enyne compounds. ► Reaction proceeded smoothly in the presence of amine oxide. ► Allyl CF3-propargyl ethers afforded adducts as a single isomer.

Treatment of various fluorinated internal alkynes with 10 mol% of RhCl3·H2O and 30 mol% of i-Pr2NEt in toluene at the reflux temperature for 18 h gave the corresponding trimerization products as an isomeric mixture in high yields. Cycloaddition using 1.0 equiv. of fluorinated alkynes and 2.0 equiv. of non-fluorinated alkynes under the same reaction conditions as in the trimerization led to mono- and bis-fluoroalkylated benzene derivatives in high yields, together with small amounts of trimerization products. The reaction of fluorine-containing bispropargyl ether with non-fluorinated alkynes took place smoothly to afford the corresponding bicyclic molecules in good to high yields.

Hydrosilylation reaction of various fluoroalkylated alkynes with Et3SiH in the presence of a catalytic amount of Co2(CO)8 was investigated. The hydrosilylation of the alkynes having fluoroalkyl and aryl groups took place smoothly with good regioselectivity (ca. 80:20). In sharp contrast, the reaction of the alkynes having a fluoroalkyl group and a benzyl-type substituent, or various propargyl alcohols gave the corresponding vinylsilanes in an excellent regio- and stereoselective manner. Treatment of the vinylsilanes with various aldehydes in the presence of Zn(OTf)2 and TBAF afforded the coupling products in good yields.

Treatment of (E)-4,4,4-trifluoro-1-aryl-2-buten-1-one with various aryldiazonium salts in the presence of palladium catalyst gave the corresponding α-arylated Heck adducts with high regio- and stereoselectivity in good to high yields.Treatment of (E)-4,4,4-trifluoro-1-aryl-2-buten-1-one with various aryldiazonium salts in the presence of palladium catalyst gave the corresponding α-arylated Heck adducts with high regio- and stereoselectivity in good to high yields.

The one-pot synthesis of trisubstituted alkenes starting from fluoroalkylated internal alkynes was investigated. Hydroboration of the alkynes proceeded in a highly regio- and stereoselective manner to give the corresponding vinylboranes in excellent yields. Without isolation, treatment of the vinylboranes with various aryl halides under the Suzuki–Miyaura cross-coupling conditions gave the fluoroalkylated trisubstituted alkenes in high yields with complete retention of the olefinic geometry.

The allylic substitution reaction of α-fluoroalkylated allyl mesylates with various carbon nucleophiles in the presence of transition metal catalyst (Pd and Mo) proceeded with high regioselectivity to give the corresponding γ-fluoroalkylated products in excellent yields.

The allylic substitution reactions of various chiral α-fluoroalkylated mesylates with carboxylic acids in the presence of a palladium catalyst proceeded smoothly to give γ-fluoroalkylated allyl esters in excellent yields. The esters were subsequently subjected to Ireland–Claisen rearrangement without isolation, leading to the corresponding homochiral α-fluoroalkylated-β,γ-unsaturated amino acids in good yields.GraphicMethyl (2S,3R)-(E)-2-(t-butoxycarbamoyl)-3-trifluoromethylundec-4-enoateC18H30F3NO4E.e.=92%[α]D22=+12.5 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: 2S,3RMethyl (2S,3R)-(E)-2-(t-butoxycarbamoyl)-3-trifluoromethylundec-4-enoateC18H31F2NO4E.e.=84%[α]D22=+5.3 (c 1.1, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: 2S,3R

Hydrosilylation reaction of various fluoroalkylated alkynes with Et3SiH in the presence of a catalytic amount of Co2(CO)8 was investigated. The hydrosilylation of the alkynes having fluoroalkyl and aryl groups took place smoothly with good regioselectivity (ca. 80:20). In sharp contrast, the reaction of the alkynes having a fluoroalkyl group and a benzyl-type substituent, or various propargyl alcohols gave the corresponding vinylsilanes in an excellent regio- and stereoselective manner. Treatment of the vinylsilanes with various aldehydes in the presence of Zn(OTf)2 and TBAF afforded the coupling products in good yields.

Treatment of various fluorinated internal alkynes with 10 mol% of RhCl3·H2O and 30 mol% of i-Pr2NEt in toluene at the reflux temperature for 18 h gave the corresponding trimerization products as an isomeric mixture in high yields. Cycloaddition using 1.0 equiv. of fluorinated alkynes and 2.0 equiv. of non-fluorinated alkynes under the same reaction conditions as in the trimerization led to mono- and bis-fluoroalkylated benzene derivatives in high yields, together with small amounts of trimerization products. The reaction of fluorine-containing bispropargyl ether with non-fluorinated alkynes took place smoothly to afford the corresponding bicyclic molecules in good to high yields.

Treatment of γ-fluoroallylic phosphate with various lower-ordered cyanocuprates derived from Grignard reagents, organolithium, and organozincs gave the corresponding SN2′ products having a fluorine atom at a quaternary carbon center in excellent yields. This system could be successfully extended to the chiral version, enantiomerically pure fluorine-containing materials also being obtained in high yield.

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]BF4 and 6 mol% of (S)-BINAP in toluene/H2O (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.