17312-57-1Relevant articles and documents
Indium Tribromide-Catalysed Transfer-Hydrogenation: Expanding the Scope of the Hydrogenation and of the Regiodivergent DH or HD Addition to Alkenes
Li, Luomo,Hilt, Gerhard
supporting information, p. 11221 - 11225 (2021/06/25)
The transfer-hydrogenation as well as the regioselective and regiodivergent addition of H?D from regiospecific deuterated dihydroaromatic compounds to a variety of 1,1-di- and trisubstituted alkenes was realised with InBr3 in dichloro(m)ethane. In comparison with the previously reported BF3?Et2O-catalysed process, electron-deficient aryl-substituents can be applied reliably and thereby several restrictions could be lifted, and new types of substrates could be transformed successfully in hydrodeuterogenation as well as deuterohydrogenation transfer-hydrogenation reactions.
Copper-Catalyzed Regioselective Hydroalkylation of 1,3-Dienes with Alkyl Fluorides and Grignard Reagents
Iwasaki, Takanori,Shimizu, Ryohei,Imanishi, Reiko,Kuniyasu, Hitoshi,Kambe, Nobuaki
supporting information, p. 9347 - 9350 (2015/08/06)
Copper complexes generated in situ from CuCl2, alkyl Grignard reagents, and 1,3-dienes play important roles as catalytic active species for the 1,2-hydroalkylation of 1,3-dienes by alkyl fluorides through C-F bond cleavage. The alkyl group is introduced to an internal carbon atom of the 1,3-diene regioselectively, thus giving rise to the branched terminal alkene product. Making the switch: A copper-hydride species, generated by the treatment of a copper salt with alkyl Grignard reagents, catalyzes the 1,2-hydroalkylation of 1,3-dienes by alkyl fluorides and Grignard reagents. The alkyl group of the alkyl fluoride is selectively introduced to an internal carbon atom of the 1,3-diene and the Grignard reagent acts as hydride source to give the branched terminal alkene, even in the presence of alkenes and alkynes.
Copper-catalyzed alkyl-alkyl cross-coupling reactions using hydrocarbon additives: Efficiency of catalyst and roles of additives
Iwasaki, Takanori,Imanishi, Reiko,Shimizu, Ryohei,Kuniyasu, Hitoshi,Terao, Jun,Kambe, Nobuaki
, p. 8522 - 8532 (2015/01/08)
Cross-coupling of alkyl halides with alkyl Grignard reagents proceeds with extremely high TONs of up to 1230000 using a Cu/unsaturated hydrocarbon catalytic system. Alkyl fluorides, chlorides, bromides, and tosylates are all suitable electrophiles, and a TOF as high as 31200 h-1 was attained using an alkyl iodide. Side reactions of this catalytic system, i.e., reduction, dehydrohalogenation (elimination), and the homocoupling of alkyl halides, occur in the absence of additives. It appears that the reaction involves the β-hydrogen elimination of alkylcopper intermediates, giving rise to olefins and Cu-H species, and that this process triggers both side reactions and the degradation of the Cu catalyst. The formed Cu-H promotes the reduction of alkyl halides to give alkanes and Cu-X or the generation of Cu(0), probably by disproportionation, which can oxidatively add to alkyl halides to yield olefins and, in some cases, homocoupling products. Unsaturated hydrocarbon additives such as 1,3-butadiene and phenylpropyne play important roles in achieving highly efficient cross-coupling by suppressing β-hydrogen elimination, which inhibits both the degradation of the Cu catalyst and undesirable side reactions.
Zirconium-catalyzed reaction of terminal alkenes with triethylindium
Ramazanov,Dil'Mukhametova,Dzhemilev
, p. 1253 - 1256 (2013/11/06)
Terminal alkenes (undec-1-ene, oct-1-ene, and allylbenzene) reacted with triethylindium in the presence of a catalytic amount of Cp2ZrCl 2 in hexane to give mixtures of three organoindium compounds whose hydrolysis in D2O afforded 2-substituted 1,4-dideuterobutane containing minor amounts of 2-substituted 1- and 4-deuterobutanes.
Co-catalyzed cross-coupling of alkyl halides with tertiary alkyl Grignard reagents using a 1,3-butadiene additive
Iwasaki, Takanori,Takagawa, Hiroaki,Singh, Surya P.,Kuniyasu, Hitoshi,Kambe, Nobuaki
supporting information, p. 9604 - 9607 (2013/07/26)
The cobalt-catalyzed cross-coupling of alkyl (pseudo)halides with alkyl Grignard reagents in the presence of 1,3-butadiene as a ligand precursor and LiI is described. Sterically congested quaternary carbon centers could be constructed by using tertiary alkyl Grignard reagents. This reaction proceeds via an ionic mechanism with inversion of stereochemistry at the reacting site of the alkyl halide and is compatible with various functional groups. The use of both 1,3-butadiene and LiI was essential for achieving high yields and high selectivities.
Novel method for generation of secondary organozinc reagent: Application to tandem carboncarbon bond formation reaction of 1,1-dibromoalkane
Harada, Toshiro,Kotani, Yasuo,Katsuhira, Takeshi,Oku, Akira
, p. 1573 - 1576 (2007/10/02)
Reaction of 1,1-dibromoalkane (R1CHBr2) with trialkylzincate ((R2)3ZnLi) followed by a palladium catalyzed coupling reaction of the resulting secondary organozinc reagent (R1CH(R2)ZnL) with various electrophiles (El-X) afforded R1CH(R2)El.
