15177-05-6Relevant articles and documents
Stereoselective photochemical reaction of cyclohexyl phenyl ketone within lytropic liquid crystals formed by chiral ionic liquids
Yang, Xiujie,Li, Xinwei,Chen, Bin,Wu, Lizhu,Zhang, Liping,Zheng, Liqiang,Tung, Chenho
, p. 603 - 606 (2013)
Irradiation of cyclohexyl phenyl ketone (1) results in either intra- or intermolecular hydrogen abstraction to afford compounds 1-phenylhept-6-en-1-one (2) and α-cyclohexyl benzyl alcohol (3) as photoproducts, in which 3 has a pair of enantiomers. Herein,
Photochemical reaction of cyclohexyl phenyl ketone within lyotropic liquid crystals
Lv, Feng-Feng,Li, Xin-Wei,Wu, Li-Zhu,Tung, Chen-Ho
, p. 1918 - 1923 (2008)
Lyotropic liquid crystals (LCs) formed by sodium dodecyl sulfate (SDS), n-pentanol, and H2O at room temperature in their tertiary phase diagram have been explored as a confined medium for the typical photochemical reaction of cyclohexyl phenyl ketone (1), which can lead to either intramolecular hydrogen abstraction product 2 or intermolecular reduction product 3 in isotropic solutions upon irradiation. Studies on the product distributions of ketone 1 in the absence and presence of electron donors in this work demonstrate that LC not only restricts the movement of the substrates and intermediates but also encapsulates the substrates and electron donors together during photoirradiation, thereby giving rise to the formation of intermolecular hydrogen abstraction product 3 with high efficiency. A comparison of the same reaction in SDS micelle reveals that LC provides much better constraint than the micelles. The solution-like LC can be used as a microreactor to direct the reaction pathway of ketone 1 by controlling the viscosity and close contact between substrates and electron donors.
Enantioselective photoreduction of arylalkyl ketones via restricting the reaction to chirally modified zeolite cages
Shailaja,Ponchot, Keith J.,Ramamurthy
, p. 937 - 940 (2000)
(equation presented) Obtaining a high enantiomeric excess during a photoreaction within a zeolite is hampered by the statistical distribution of reactant and chiral inductor molecules within the cages of a zeolite. By restricting the photoreactions to onl
Copper-Catalyzed Intramolecular Amination of C(sp3)-H Bond of Secondary Amines to Access Azacycles
Jin, Ruo-Xing,Dai, Jing-Cheng,Li, Yan,Wang, Xi-Sheng
supporting information, p. 421 - 426 (2021/01/26)
The cross-coupling of C-N bond directly from inert C-H bonds is an ideal approach to synthesize saturated azacycles due to its high efficiency and atom economy. In this article, a copper-catalyzed intramolecular amination via the cross coupling of C(sp3)-H and N-H bonds of secondary amine has been reported, which exhibit excellent chemo- and regioselectivity, extensive substrate scope, and functional group tolerance in good to excellent yield, offering an efficient pathway to build nitrogen-containing heterocycle skeletons.
Vinyl Azides as Radical Acceptors in the Vitamin B12-Catalyzed Synthesis of Unsymmetrical Ketones
Dworakowski, Krzysztof R.,Pisarek, Sabina,Hassan, Sidra,Gryko, Dorota
supporting information, p. 9068 - 9072 (2021/11/30)
Vinyl azides are very reactive species and as such are useful building blocks, in particular, in the synthesis of N-heterocycles. They can also serve as precursors of ketones. These form in reactions of vinyl azides with nucleophiles or radicals. We have found, however, that under light irradiation vitamin B12 catalyzes the reaction of vinyl azides with electrophiles to afford unsymmetrical carbonyl compounds in decent yields. Mechanistic studies revealed that alkyl radicals are key intermediates in this transformation.
From selective transfer hydrogenation to selective hydrogen auto-transfer process: An efficient method for the synthesis of alkenyl ketones via iridium-catalyzed α-alkylation of ketones with alkenyl alcohols
Li, Feng,Li, Shun,Meng, Chong,Xu, Xiangchao,Yang, Chenchen,Yang, Jiazhi,Yu, Junjie
, p. 335 - 343 (2021/10/07)
A strategy for the synthesis of alkenyl ketones via the α-alkylation of ketones with alkenyl ketones has proposed and accomplished. In the presence of a metal–ligand bifunctional catalyst [Cp*Ir(2,2′-bpyO)(H2O)], a series of desirable products
Aminoalkyl radicals as halogen-atom transfer agents for activation of alkyl and aryl halides
Constantin, Timothée,Juliá, Fabio,Leonori, Daniele,Regni, Alessio,Sheikh, Nadeem S.,Zanini, Margherita
, p. 1021 - 1026 (2020/03/10)
Organic halides are important building blocks in synthesis, but their use in (photo)redox chemistry is limited by their low reduction potentials. Halogen-atom transfer remains the most reliable approach to exploit these substrates in radical processes despite its requirement for hazardous reagents and initiators such as tributyltin hydride. In this study, we demonstrate that a-aminoalkyl radicals, easily accessible from simple amines, promote the homolytic activation of carbon-halogen bonds with a reactivity profile mirroring that of classical tin radicals. This strategy conveniently engages alkyl and aryl halides in a wide range of redox transformations to construct sp3-sp3, sp3-sp2, and sp2-sp2 carbon-carbon bonds under mild conditions with high chemoselectivity.
Iminyl Radicals by Reductive Cleavage of N-O Bond in Oxime Ether Promoted by SmI2: A Straightforward Synthesis of Five-Membered Cyclic Imines
Huang, Fei,Zhang, Songlin
supporting information, p. 7430 - 7434 (2019/10/11)
A new generation method of N-centered radicals from the reductive cleavage of the N-O bond in oxime ether promoted by SmI2 is reported for the first time. The in-situ-generated N-centered radicals underwent intramolecular cyclization to afford five-membered cyclic imines in two manners: N-centered radical addition and N-centered anion nucleophilic substitution. From a synthetic point of view, an efficient synthetic method of five-membered cyclic imines was developed. A mechanism of the transformation was proposed.
Cu/Mn bimetallic catalysis enables carbonylative Suzuki-Miyaura coupling with unactivated alkyl electrophiles
Pye, Dominic R.,Cheng, Li-Jie,Mankad, Neal P.
, p. 4750 - 4755 (2017/07/10)
A bimetallic system consisting of Cu-carbene and Mn-carbonyl co-catalysts was employed for carbonylative C-C coupling of arylboronic esters with alkyl halides, allowing for the convergent synthesis of ketones. The system operates under mild conditions and exhibits complementary reactivity to Pd catalysis. The method is compatible with a wide range of arylboronic ester nucleophiles and proceeds smoothly for both primary and secondary alkyl iodide electrophiles. Preliminary mechanistic experiments corroborate a hypothetical catalytic mechanism consisting of co-dependent cycles wherein the Cu-carbene co-catalyst engages in transmetallation to generate an organocopper nucleophile, while the Mn-carbonyl co-catalyst activates the alkyl halide electrophile by single-electron transfer and then undergoes reversible carbonylation to generate an acylmanganese electrophile. The two cycles then intersect with a heterobimetallic, product-releasing C-C coupling step.
Iron-Catalyzed Regioselective Oxo- and Hydroxy-Phthalimidation of Styrenes: Access to α-Hydroxyphthalimide Ketones
Zhang, Ji-Zong,Tang, Yu
, p. 752 - 764 (2016/03/09)
This paper describes the aerobic oxidation of styrenes catalyzed by iron(III) chloride (FeCl3) to form β-keto-N-alkoxyphthalimides in fair to good yields. This oxidative process employs mild conditions with green and atom efficient dioxygen (O2) as the oxidant.
