- A novel synthesis of trifluoromethylated multi-substituted alkenes via regio- and stereoselective Heck reaction of (E)-4,4,4-trifluoro-1-phenyl-2- buten-1-one
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Treatment of (E)-4,4,4-trifluoro-1-phenyl-2-buten-1-one with various aryldiazonium salts in the presence of a palladium catalyst led to a smooth Heck reaction, furnishing α-arylated adducts in good yields. Georg Thieme Verlag Stuttgart.
- Konno, Tsutomu,Yamada, Shigeyuki,Tani, Akinori,Miyabe, Tomotsugu,Ishihara, Takashi
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- Photocatalytic hydroacylation of trifluoromethyl alkenes
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Hydrofunctionalization of trifluoromethyl alkenes is highly challenging, because the nucleophilic addition is oftentimes followed by β-F elimination in this case. By the use of tetrabutylammonium decatungstate (TBADT) as a hydrogen-atom-transfer (HAT) photocatalyst for acyl C-H activation, we successfully avoid the β-F elimination in the hydroacylation of trifluoromethyl alkenes with aldehydes. This light (390 nm) promoted reaction provides a facile and efficient access to various β-CF3 ketones in complete regiocontrol with high functionality tolerance and 100% atom economy.
- Fan, Pei,Zhang, Chang,Lan, Yun,Lin, Zhiyang,Zhang, Linchuan,Wang, Chuan
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supporting information
p. 12691 - 12694
(2019/10/28)
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- Base-promoted isomerization of CF3-containing allylic alcohols to the corresponding saturated ketones under metal-free conditions
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Following to the computational expectation, our previously reported intriguing 1,3-proton shift of 4,4,4-trifluorobut-2-yn-1-ols was successfully extended to the 4,4,4-trifluorobut-2-en-1-ol system under metal-free conditions to afford the corresponding saturated ketones in high to excellent chemical yields using such a convenient and easy-to-handle base as DBU at the toluene refluxing temperature, and utilization of the corresponding optically active substrates unambiguously demonstrated that this transformation proceeded in a highly stereoselective fashion.
- Hamada, Yoko,Kawasaki-Takasuka, Tomoko,Yamazaki, Takashi
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p. 1507 - 1512
(2017/08/14)
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- Base-Catalyzed Stereospecific Isomerization of Electron-Deficient Allylic Alcohols and Ethers through Ion-Pairing
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A mild base-catalyzed strategy for the isomerization of allylic alcohols and allylic ethers has been developed. Experimental and computational investigations indicate that transition metal catalysts are not required when basic additives are present. As in the case of using transition metals under basic conditions, the isomerization catalyzed solely by base also follows a stereospecific pathway. The reaction is initiated by a rate-limiting deprotonation. Formation of an intimate ion pair between an allylic anion and the conjugate acid of the base results in efficient transfer of chirality. Through this mechanism, stereochemical information contained in the allylic alcohols is transferred to the ketone products. The stereospecific isomerization is also applicable for the first time to allylic ethers, yielding synthetically valuable enantioenriched (up to 97% ee) enol ethers.
- Martinez-Erro, Samuel,Sanz-Marco, Amparo,Bermejo Gómez, Antonio,Vázquez-Romero, Ana,Ahlquist, M?rten S. G.,Martín-Matute, Belén
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p. 13408 - 13414
(2016/10/22)
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- Regioselective 1,4-trifluoromethylation of α,β-unsaturated ketones via a S-(trifluoromethyl)diphenylsulfonium salts/copper system
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Regioselective conjugate 1,4-trifluoromethylation of α,β- unsaturated ketones by the use of shelf-stable electrophilic trifluoromethylating reagents, S-(trifluoromethyl)diphenylsulfonium salts and copper under mild conditions is described. A wide range of acyclic aryl-aryl-enones and aryl-alkyl-enones were converted into β- trifluoromethylated ketones in low to moderate yields.
- Okusu, Satoshi,Sugita, Yutaka,Tokunaga, Etsuko,Shibata, Norio
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supporting information
p. 2189 - 2193
(2013/11/19)
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- Iron(II) complexes are suitable catalysts for the isomerization of trifluoromethylated allylic alcohols. Synthesis of trifluoromethylated dihydrochalcones
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We demonstrated that iron(II) complexes can substitute platinum metals as well as iron(0) carbonyls for the isomerization of γ-trifluoromethylated allylic alcohols into β-trifluoromethylated ketones. In particular, iron(II)-tetra(isonitrile) complexes were employed for the synthesis of a series of trifluoromethylated dihydrochalcones variously decorated on each aromatic ring.
- Cahard, Dominique,Bizet, Vincent,Dai, Xiaoyang,Gaillard, Sylvain,Renaud, Jean-Luc
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supporting information
p. 78 - 82
(2013/10/01)
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- Rhodium(i)-catalyzed 1,4-conjugate arylation toward β-fluoroalkylated electron-deficient alkenes: A new entry to a construction of a tertiary carbon center possessing a fluoroalkyl group
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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]BF4 and 6 mol% of (S)-BINAP in toluene/H 2O (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.
- Morigaki, Atsunori,Tanaka, Tomoo,Miyabe, Tomotsugu,Ishihara, Takashi,Konno, Tsutomu
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p. 586 - 595
(2013/03/14)
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- Synthesis of β-CF3 ketones from trifluoromethylated allylic alcohols by ruthenium catalyzed isomerization
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This work describes the optimization process for the synthesis of β-trifluoromethylated ketones from trifluoromethylated allylic alcohols. This transformation proceeds through a ruthenium catalyzed isomerization under mild conditions with high atom econom
- Bizet, Vincent,Pannecoucke, Xavier,Renaud, Jean-Luc,Cahard, Dominique
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- Ruthenium-catalyzed redox isomerization of trifluoromethylated allylic alcohols: Mechanistic evidence for an enantiospecific pathway
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Transfer news: A synthetic approach to chiral β-CF3- substituted saturated carbonyl compounds has been developed in which ruthenium complexes efficiently catalyze the redox isomerization of CF3-bearing allylic alcohols by an intramol
- Bizet, Vincent,Pannecoucke, Xavier,Renaud, Jean-Luc,Cahard, Dominique
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p. 6467 - 6470
(2012/07/27)
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- Unexpected high regiocontrol in Heck reaction of fluorine-containing electron-deficient olefins-Highly regio- and stereoselective synthesis of β-fluoroalkyl-α-aryl-α,β-unsaturated ketones
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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.
- Konno, Tsutomu,Yamada, Shigeyuki,Tani, Akinori,Nishida, Masataka,Miyabe, Tomotsugu,Ishihara, Takashi
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experimental part
p. 913 - 921
(2010/01/15)
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