153389-13-0Relevant academic research and scientific papers
A New C-C Bond-forming Free Radical Rearrangement
Crich, David,Yao, Qingwei
, p. 1265 - 1267 (1993)
On treatment with tributyltin hydride and azoisobutyronitrile in benzene at reflux α-aryl-β-bromoalkyl vinyl ethers rearrange in moderate yield to δ-aryl ketones: possible mechanistic rationales are discussed for this novel C-C bond-forming process.
Cross-Coupling of Amides with Alkylboranes via Nickel-Catalyzed C-N Bond Cleavage
Liu, Xiangqian,Hsiao, Chien-Chi,Guo, Lin,Rueping, Magnus
, p. 2976 - 2979 (2018)
A protocol for the nickel-catalyzed alkylation of amides was established. The use of alkylboranes as nucleophilic partners allowed the use of mild reaction conditions and compatibility of various functional groups with respect to both coupling partners. The catalytic alkylation proceeded selectively at the amides in the presence of other functional groups as well as other carboxylic acid derived moieties.
Nickel-Catalyzed Cross-Coupling of Aryl Pivalates with Cyclobutanols Involving C—O and C—C Bond Cleavage?
Gan, Yi,Zhang, Ninghui,Huang, Shaoxu,Liu, Yuanhong
supporting information, p. 1686 - 1690 (2020/11/03)
An efficient nickel-catalyzed cross-coupling of aryl pivalates with cyclobutanols is described. The use of Ni(cod)2/PCy3/base as the catalytic system enables the cleavage of inert C—O bond and C—C bond under mild conditions, thus providing a facile access to γ-arylated ketones in generally good to excellent yields. This transformation is also characterized by wide substrate scope and functional group compatibility, for example, methoxy, N,N-dimethylamino, keto, ester, fluoro and TMS groups are well-tolerated during the reaction process.
A metal-free desulfurizing radical reductive C-C coupling of thiols and alkenes
Qin, Qixue,Wang, Weijing,Zhang, Cheng,Song, Song,Jiao, Ning
supporting information, p. 10583 - 10586 (2019/09/06)
An intermolecular reductive C-C coupling of electrophilic alkyl radicals and alkenes has been developed. Thiols were used as both hydrogen-donating reagents and alkyl radical precursors in the presence of triethyl phosphite and radical initiator. A wide range of alkenes, including styrenes, and aliphatic olefins were well tolerated in this transformation. Mechanistic studies indicated that a phosphite promoted radical desulfurization of thiols to access electrophilic alkyl radicals and a radical chain propagation process may be involved in this transformation.
Iron-Catalysed Remote C(sp3)?H Azidation of O-Acyl Oximes and N-Acyloxy Imidates Enabled by 1,5-Hydrogen Atom Transfer of Iminyl and Imidate Radicals: Synthesis of γ-Azido Ketones and β-Azido Alcohols
Torres-Ochoa, Rubén O.,Leclair, Alexandre,Wang, Qian,Zhu, Jieping
supporting information, p. 9477 - 9484 (2019/05/21)
In the presence of a catalytic amount of iron(III) acetylacetonate [Fe(acac)3], the reaction of structurally diverse ketoxime esters with trimethylsilyl azide (TMSN3) afforded γ-azido ketones in good to excellent yields. This unprecedented distal γ-C(sp3)?H bond azidation reaction went through a sequence of reductive generation of an iminyl radical, 1,5-hydrogen atom transfer (1,5-HAT) and iron-mediated redox azido transfer to the translocated carbon radical. TMSN3 served not only as a nitrogen source to functionalise the unactivated C(sp3)?H bond, but also as a reductant to generate the catalytically active FeII species in situ. Based on the same principle, a novel β-C(sp3)?H functionalisation of alcohols via N-acyloxy imidates was subsequently realised, leading, after hydrolysis of the resulting ester, to β-azido alcohols, which are important building blocks in organic and medicinal chemistry.
Metal-free visible light photoredox enables generation of carbyne equivalents via phosphonium ylide C-H activation
Das, Mrinmoy,Vu, Minh Duy,Zhang, Qi,Liu, Xue-Wei
, p. 1687 - 1691 (2019/02/14)
Carbyne, an interesting synthetic intermediate, has recently been generated from hypervalent iodine precursors via photoredox catalysis. Given the underexplored chemistry of carbyne, due to the paucity of carbyne sources, we are intrigued to discover a new source for this reactive species from classical reagents-phosphonium ylides. Our novel strategy employing phosphonium ylides in an olefin hydrocarbonation reaction features a facile approach for constructing carbon-carbon bonds through metal-free and benign reaction conditions. Moreover, the hydrocarbonation products were delivered in a highly regioselective manner.
Ligand-Controlled Chemoselective C(acyl)-O Bond vs C(aryl)-C Bond Activation of Aromatic Esters in Nickel Catalyzed C(sp2)-C(sp3) Cross-Couplings
Chatupheeraphat, Adisak,Liao, Hsuan-Hung,Srimontree, Watchara,Guo, Lin,Minenkov, Yury,Poater, Albert,Cavallo, Luigi,Rueping, Magnus
, p. 3724 - 3735 (2018/03/21)
A ligand-controlled and site-selective nickel catalyzed Suzuki-Miyaura cross-coupling reaction with aromatic esters and alkyl organoboron reagents as coupling partners was developed. This methodology provides a facile route for C(sp2)-C(sp3) bond formation in a straightforward fashion by successful suppression of the undesired β-hydride elimination process. By simply switching the phosphorus ligand, the ester substrates are converted into the alkylated arenes and ketone products, respectively. The utility of this newly developed protocol was demonstrated by its wide substrate scope, broad functional group tolerance and application in the synthesis of key intermediates for the synthesis of bioactive compounds. DFT studies on the oxidative addition step helped rationalizing this intriguing reaction chemoselectivity: whereas nickel complexes with bidentate ligands favor the C(aryl)-C bond cleavage in the oxidative addition step leading to the alkylated product via a decarbonylative process, nickel complexes with monodentate phosphorus ligands favor activation of the C(acyl)-O bond, which later generates the ketone product.
Photoredox-Catalyzed Decarboxylative Alkylation of Silyl Enol Ethers to Synthesize Functionalized Aryl Alkyl Ketones
Kong, Weiguang,Yu, Changjiang,An, Hejun,Song, Qiuling
, p. 349 - 352 (2018/01/28)
Photoredox-catalyzed decarboxylative alkylation of silyl enol ethers has been developed. Diverse functionalized aryl alkyl ketones were afforded in modest to good yields using N-(acyloxy)phthalimide as an easy access alkyl radical source under mild and operationally simple conditions. The excellent performance of drug molecules such as fenbufen and indomethacin and naturally occurring carboxylic acids such as stearic acid and dehydrocholic acid further demonstrated the practicability of the reaction.
Titanocene(III) chloride mediated reductive cleavage of arylcyclopropyl ketones
Paira,Mandal,Roy
experimental part, p. 573 - 577 (2010/12/25)
Titanocene(III) chloride (Cp2TiCl) mediated cleavage of arylcyclopropyl ketones has been accomplished. Both saturated and β-H eliminated unsaturated aromatic compounds are formed in different ratio depending on the substrate. Ti(III) species has been prepared in situ from commercially available titanocene dichloride (Cp2TiCl2) and zinc dust in THF.
Nickel-catalyzed borylation of aryl cyclopropyl ketones with bis(pinacolato)diboron to synthesize 4-oxoalkylboronates
Sumida, Yuto,Yorimitsu, Hideki,Oshima, Koichiro
supporting information; experimental part, p. 3196 - 3198 (2009/08/08)
Aryl cyclopropyl ketones undergo nickel-catalyzed borylative ring opening with bis(pinacolato)diboron to yield 4-oxoalkylboronates.
