19956-03-7Relevant academic research and scientific papers
Palladium-Catalyzed Markovnikov Hydroaminocarbonylation of 1,1-Disubstituted and 1,1,2-Trisubstituted Alkenes for Formation of Amides with Quaternary Carbon
Yang, Hui-Yi,Yao, Ya-Hong,Chen, Ming,Ren, Zhi-Hui,Guan, Zheng-Hui
supporting information, p. 7298 - 7305 (2021/05/26)
Hydroaminocarbonylation of alkenes is one of the most promising yet challenging methods for the synthesis of amides. Herein, we reported the development of a novel and effective Pd-catalyzed Markovnikov hydroaminocarbonylation of 1,1-disubstituted or 1,1,2-trisubstituted alkenes with aniline hydrochloride salts to afford amides bearing an α quaternary carbon. The reaction makes use of readily available starting materials, tolerates a wide range of functional groups, and provides a facile and straightforward approach to a diverse array of amides bearing an α quaternary carbon. Mechanistic investigations suggested that the reaction proceeded through a palladium hydride pathway. The hydropalladation and CO insertion are reversible, and the aminolysis is probably the rate-limiting step.
Electrochemistry enabled selective vicinal fluorosulfenylation and fluorosulfoxidation of alkenes
Jiang, Yimin,Shi, Zhaojiang,Wu, Jinnan,Wu, Shaofen,Ye, Keyin,Yu, Yi,Yuan, Yaofeng
supporting information, (2021/11/17)
Both sulfur and fluorine play important roles in organic synthesis, the life science, and materials science. The direct incorporation of these elements into organic scaffolds with precise control of the oxidation states of sulfur moieties is of great significance. Herein, we report the highly selective electrochemical vicinal fluorosulfenylation and fluorosulfoxidation reactions of alkenes, which were enabled by the unique ability of electrochemistry to dial in the potentials on demand. Preliminary mechanistic investigations revealed that the fluorosulfenylation reaction proceeded through a radical-polar crossover mechanism involving a key episulfonium ion intermediate. Subsequent electrochemical oxidation of fluorosulfides to fluorosulfoxides were readily achieved under a higher applied potential with the adventitious H2O in the reaction mixture.
Additions of Aldehyde-Derived Radicals and Nucleophilic N-Alkylindoles to Styrenes by Photoredox Catalysis
Klussmann, Martin,Lux, Marcel
supporting information, (2020/04/30)
The consecutive addition of acyl radicals and N-alkylindole nucleophiles to styrenes was established, as well as some additional radical-nucleophile combinations. Both aryl and aliphatic aldehydes give reasonable yields. The reaction proceeds best for α-substituted styrenes, effectively creating a quaternary all-carbon center. Some iridium-based photoredox systems are catalytically active; furthermore, a base is needed in this transformation. Radicals are formed by reductive perester cleavage and hydrogen atom transfer.
Iodobenzene-catalyzed oxidative cleavage of olefins to carbonyl compounds
Du, Lele,Wang, Zechao,Wu, Junliang
supporting information, (2020/07/20)
A metal-free approach for the oxidative cleavage of carbon–carbon double bonds of olefins to carbonyl compounds was established by using oxidant m-CPBA and non-metallic organocatalyst PhI in toluene/H2O. A broad scope of aromatic olefins was used. All the reactions proceeded smoothly at 35 °C in short reaction time to furnish the respective mono- and double carbonyl compounds selectively in moderate to good yields.
Regioselective Diboron-Mediated Semireduction of Terminal Allenes
Gates, Ashley M.,Santos, Webster L.
supporting information, p. 4619 - 4624 (2019/12/11)
A method for the regioselective reduction of the terminal double bond of 1,1-disubstituted allenes has been developed. In the presence of a palladium catalyst, tetrahydroxydiboron and stoichiometric water, allene semireduction proceeds in high yield to afford Z-alkenes selectively.
Towards nitrile-substituted cyclopropanes-a slow-release protocol for safe and scalable applications of diazo acetonitrile
Hock, Katharina J.,Spitzner, Robin,Koenigs, Rene M.
supporting information, p. 2118 - 2122 (2017/07/24)
Diazo acetonitrile has long been neglected despite its high value in organic synthesis due to a high risk of explosions. Herein, we report our efforts towards the transient and safe generation of this diazo compound, its applications in iron catalyzed cyclopropanation and cyclopropenation reactions and the gram-scale synthesis of cyclopropyl nitriles.
Synthesis of 2,5-Diaryl-1,5-dienes from Allylic Bromides Using Visible-Light Photoredox Catalysis
Pratsch, Gerald,Overman, Larry E.
, p. 11388 - 11397 (2015/12/01)
Visible-light photoreductive coupling of 2-arylallyl bromides in the presence of the photocatalyst Ru(bpy)3(PF6)2, a Hantzsch ester, and i-Pr2NEt gives 2,5-diaryl-1,5-dienes in high yield. This method avoids the use of stoichiometric metal reductants and is compatible with the presence of halogen, alkyl, electron-donating, and electron-withdrawing substituents on the aromatic ring.
Method for synthesizing (E)-Anethol and Related Compounds By Cross Coupling Reaction of Potassium alllyltrifluroborate and 4-bromoanisole and aryl halides
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Page/Page column 4, (2012/01/15)
Methods of producing substituted and non-substituted beta-methyl styrene by a cross-coupling reaction are provided. The disclosure also provides for methods of preparing (E)-Anethol and related compounds by a cross coupling reaction of potassium allyltrifluoroborate and 4-bromoanisole and aryl halides. Compounds, compositions, and methods of treating disorders utilizing beta-methyl styrene are also provided.
Readily available hydrogen bond catalysts for the asymmetric transfer hydrogenation of nitroolefins
Schneider, Jakob F.,Lauber, Markus B.,Muhr, Vanessa,Kratzer, Domenic,Paradies, Jan
supporting information; experimental part, p. 4323 - 4327 (2011/07/08)
This paper focuses on readily accessible thiourea hydrogen bond catalysts derived from amino acids, whose steric and electronic features are modulated by their degree of substitution at the carbinol carbon center. These catalysts were applied in the asymmetric transfer hydrogenation of nitroolefins furnishing the chiral products in up to 99% yield and 86% enantiomeric excess. The proposed catalyst's mode of action is supported by mechanistic investigations.
Nickel-catalyzed heck-type reactions of benzyl chlorides and simple olefins
Matsubara, Ryosuke,Gutierrez, Alicia C.,Jamison, Timothy F.
supporting information; experimental part, p. 19020 - 19023 (2011/12/21)
Nickel-catalyzed intermolecular benzylation and heterobenzylation of unactivated alkenes to provide functionalized allylbenzene derivatives are described. A wide range of both the benzyl chloride and alkene coupling partners are tolerated. In contrast to analogous palladium-catalyzed variants of this process, all reactions described herein employ electronically unbiased aliphatic olefins (including ethylene), proceed at room temperature, and provide 1,1-disubstituted olefins over the more commonly observed 1,2-disubstituted olefins with very high selectivity.
