23033-63-8Relevant academic research and scientific papers
Fe-Catalyzed decarbonylative alkylation-peroxidation of alkenes with aliphatic aldehydes and hydroperoxide under mild conditions
Wu, Chuan-Shuo,Li, Rong,Wang, Qi-Qiang,Yang, Luo
supporting information, p. 269 - 274 (2019/01/28)
A convenient Fe-catalyzed decarbonylative alkylation-peroxidation of alkenes with aliphatic aldehydes and TBHP to provide chain elongated peroxides is developed, which is further applied to the one-pot synthesis of alkylated ketones. Aliphatic aldehydes were decarbonylated into 1°, 2° and 3° alkyl radicals at low temperature which subsequently allows the cascade construction of C(sp3)-C(sp3) and C(sp3)-O bonds via radical insertion and radical-radical coupling. Various alkenes including mono-substituted, terminally disubstituted or internally disubstituted styrenes bearing synthetically useful functional groups and electron-poor acrylates were tolerated.
Regioselective Vinylation of Remote Unactivated C(sp3)?H Bonds: Access to Complex Fluoroalkylated Alkenes
Wu, Shuo,Wu, Xinxin,Wang, Dongping,Zhu, Chen
, p. 1499 - 1503 (2019/01/04)
Regioselective incorporation of a particular functional group into aliphatic sites by direct activation of unreactive C?H bonds is of great synthetic value. Despite advances in radical-mediated functionalization of C(sp3)?H bonds by a hydrogen-atom transfer process, the site-selective vinylation of remote C(sp3)?H bonds still remains underexplored. Reported herein is a new protocol for the regioselective vinylation of unactivated C(sp3)?H bonds. The remote C(sp3)?H activation is promoted by a C-centered radical instead of the commonly used N and O radicals. The reaction possesses high product diversity and synthetic efficiency, furnishing a plethora of synthetically valuable E alkenes bearing tri-/di-/mono-fluoromethyl and perfluoroalkyl groups.
Iron-Catalyzed Oxyalkylation of Terminal Alkynes with Alkyl Iodides
Deng, Weili,Ye, Changqing,Li, Yajun,Li, Daliang,Bao, Hongli
supporting information, p. 261 - 265 (2019/01/10)
A general oxyalkylation of terminal alkynes enabled by iron catalysis has been developed. Primary and secondary alkyl iodides acted as the alkylating reagents and afforded a range of α-alkylated ketones under mild reaction conditions. Acetyl tert-butyl peroxide (TBPA) was used as the radical relay precursor, providing the initiated methyl radical to start the radical relay process. Preliminary mechanistic studies were conducted, and late-stage functionalizations of natural product derivatives were performed.
Iron-Catalyzed Radical Decarboxylative Oxyalkylation of Terminal Alkynes with Alkyl Peroxides
Zhu, Xiaotao,Ye, Changqing,Li, Yajun,Bao, Hongli
supporting information, p. 10254 - 10258 (2017/08/07)
An iron-catalyzed oxyalkylation of alkynes with alkyl peroxides as the alkylating reagents has been investigated. Alkyl peroxides are readily available from aliphatic acids and serve simultaneously as the alkylating reagents and internal oxidants. Primary, secondary, and tertiary alkyl groups of aliphatic acids were readily incorporated into C?C triple bonds and diverse α-alkylated ketones were synthesized. Mechanism studies revealed that this reaction involves highly reactive alkyl free radicals. A unique equilibrium between lauric acid and water catalyzed by the iron(III) catalyst was observed.
Oxidative C-C bond cleavage of aldehydes via visible-light photoredox catalysis
Sun, Hongnan,Yang, Chao,Gao, Fei,Li, Zhe,Xia, Wujiong
supporting information, p. 624 - 627 (2013/04/23)
The visible-light mediated oxidative C-C bond cleavage of aldehydes has been achieved in good yields at ambient temperature and open to air using Ru(bpy)3Cl2 (bpy = 2,2′-bipyridine) as the photoredox catalyst. Moreover, we further demonstrated the application in a tandem Michael/oxidative C-C bond cleavage reaction.
Palladium-catalyzed diorganozinc conjugate additions to enones: Preparative and computational studies
Lorenzo, Paula,Aurrecoechea, Jose M.,De Lera, Angel R.,Alvarez, Rosana
, p. 2621 - 2626 (2013/06/04)
The Pd-catalyzed conjugate addition of diorganozinc reagents to α,β-unsaturated carbonyl compounds has been applied to a variety of enone substrates, both cyclic and acyclic, encompassing various combinations of aryl and alkyl substitution, in combination with diorganozinc reagents incorporating alkyl (Me, linear and branched) or Ph groups. While both Pd 0 and PdII complexes have been found to be competent precatalysts, reaction yields are strongly dependent on the relative amounts of Pd to phosphane ligand. Thus, a 1:1 Pd/P ratio is well tolerated, but going to Pd/P = 1:2 leads to poor conversions and yields. A calculated Pd 0-mediated pathway involving an unusual oxidative addition step with simultaneous transmetalation, followed by reductive elimination, has been found to be compatible with the observed phosphane effect. A phosphane dependence is found in the Pd0-catalyzed diorganozinc conjugate addition to enones, which is compatible with a calculated reaction pathway proceeding through simultaneous oxidative addition/transmetalation followed by reductive elimination. Copyright
Enantioselective conjugate addition of dialkylzincs to α,β- unsaturated enones catalyzed by Ni(acac)2 and (+)-(1S,2R)-7,7- dimethyl-1-morpholinoisonorborneol
Tseng, Chih-Hao,Hung, Yu-Ming,Uang, Biing-Jiun
experimental part, p. 130 - 135 (2012/05/20)
A mixture of chiral ligand 4 [(+)-MINBOL] and Ni(acac)2 (12.5 and 0.5 mol % respectively) is able to successfully catalyze the enantioselective conjugate 1,4-addition of dialkylzinc to α,β- unsaturated enones in propionitrile to give the corres
Enantioselective 1,4-conjugate addition of diethylzinc to (E)-alkenyl aryl ketones catalysed by Cu/DiPPAM complex
Magrez, Magaly,Wencel-Delord, Joanna,Crévisy, Christophe,Mauduit, Marc
experimental part, p. 3507 - 3511 (2012/06/15)
We report here the use of the DiPPAM-L1 ligand for copper-catalysed asymmetric conjugate addition (ACA) of diethylzinc to various (E)-alkenyl aryl ketones where the aryl ring is either a phenyl group substituted by nitro, chloro or methoxy groups or not s
METHOD OF ENANTIOSELECTIVE ADDITION TO ENONES
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Page/Page column 19; 22, (2011/11/30)
The present invention relates to a method of enantioselective addition to enones, including: reacting R3(CH2)pCH═CR5C(═O)Y(CH2)qR4 with R6ZnR7 in the presen
Construction of a new type of chiral bidentate NHC ligands: copper-catalyzed asymmetric conjugate alkylation
Uchida, Tatsuya,Katsuki, Tsutomu
experimental part, p. 4741 - 4743 (2011/04/22)
We synthesized in three steps simple chiral bidentate NHC compounds that carry an achiral coordinating group as N-substituent and revealed that they serve as efficient chiral auxiliaries for the copper-catalyzed asymmetric conjugate addition of dialkylzin
