22734-04-9Relevant academic research and scientific papers
Ligand-Controlled, Tunable Copper-Catalyzed Radical Divergent Trifluoromethylation of Unactivated Cycloalkenes
Wang, Qi,Zang, Zhong-Lin,Jie, Mi,Luo, Li-Hua,Yang, Dan,Zhou, Cheng-He,Cai, Gui-Xin
supporting information, p. 5284 - 5291 (2021/10/25)
The Cu-catalyzed high-chemoselective trifluoromethylation reactions of unactivated cycloalkenes via the modulation of appropriate ligands have been explored. The Cu(I)/appropriate ligands-catalytic systems overcome the key challenge in differentiating two pathways involving radical intermediates and provide a ligand-controlled approach for site-specific spiro-aryltrifluoromethylation and chlorotrifluoromethylation to afford trifluoromethylated spiro-tetrahydroquinoline compounds and vicinal Cl-containing trifluoromethyl cycloalkanes. Moreover, compared with reported chlorine sources, 1,2-dichloroethane is used as more green and economical feedstock for chlorotrifluoromethylation. (Figure presented.).
Iridium-Catalyzed Cycloisomerization of N-Tethered 1,7-Enynes: Construction of an Azabicyclo[5.1.0]octene System
Zhao, Sheng,Zang, Zhong-Lin,Li, Siyu,Wen, Xumei,Wang, Chenhui,Guo, Jian,He, Yun
, p. 9321 - 9330 (2020/08/14)
An efficient method for the synthesis of azabicyclo[5.1.0]octenes through cycloisomerization of nitrogen-tethered 1,7-enynes catalyzed by [IrCp*Cl2]2 was developed. With appropriately designed substrates, this method could be easily employed to generate complex fused ring systems such as [6-6-3-7], [5-6-3-7], [7-6-3-7], and [8-6-3-7] ring systems, which enriches the diversity of the cyclopropane-fused polycycle library, and has potential applications in SAR studies of pharmaceutically interesting compounds and total synthesis of natural products.
Pd-Catalyzed Remote Site-Selective and Stereoselective C(Alkenyl)-H Alkenylation of Unactivated Cycloalkenes
Mao, Chun-Li,Zhao, Sheng,Zang, Zhong-Lin,Xiao, Lin,Zhou, Cheng-He,He, Yun,Cai, Gui-Xin
, p. 774 - 787 (2020/01/09)
A palladium-catalyzed alkenylation involving remote δ-position C(alkenyl)-H activation of cycloalkenes reacting with electron-deficient alkenes is described. This method features excellent site selectivity and stereoselectivity to efficiently afford only E-selective highly substituted 1,3-diene derivatives with extra-ligand-free and good functional group tolerance including estrone and free N-H tryptamine under weakly alkaline conditions. Mechanistic studies suggest that picolinamide as a bidentate directing group enables the formation of unique alkenyl palladacycle intermediates.
Regioselective intramolecular Markovnikov and anti-Markovnikov hydrofunctionalization of alkenes: Via photoredox catalysis
Li, Na,Man, Yunquan,Tang, Bo,Wang, Hongyu,Wang, Kaiye,Xiang, Yanan
supporting information, p. 11426 - 11429 (2019/09/30)
Highly regioselective Markovnikov hydrofunctionalization of alkenes was successfully realized via photoredox catalysis by introducing a urea group and fine tuning the hydrogen atom transfer catalysts. The anti-Markovnikov hydroamination of alkenes was also achieved with high yields and stereoselectivities in this work.
Corresponding amine nitrile and method of manufacturing thereof
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Paragraph 0153; 0154; 0155; 0164; 0165, (2018/05/07)
The invention relates to a manufacturing method of nitrile. Compared with the prior art, the manufacturing method has the characteristics of significantly reduced using amount of an ammonia source, low environmental pressure, low energy consumption, low production cost, high purity and yield of a nitrile product and the like, and nitrile with a more complex structure can be obtained. The invention also relates to a method for manufacturing corresponding amine from nitrile.
Copper-Catalyzed Divergent Trifluoromethylation/Cyclization of Unactivated Alkenes
Zheng, Jing,Deng, Ziyang,Zhang, Yan,Cui, Sunliang
supporting information, p. 746 - 751 (2016/03/09)
Most of the precedent copper-catalyzed trifluoromethylation reactions of unactivated alkenes concern terminal alkenes, and these processes are terminated in elimination, or nucleophilic addition, or semipinacol rearrangement, or C-H bond functionalization steps. In this study, we develop a trifluoromethylation method for both unactivated terminal and internal alkenes to enable divergent late-stage radical cyclization and achieve high molecular complexity. These cyclizations are well consistent with Baldwin's rule. Furthermore, a kinetic isotope effect (KIE) study and control reactions were conducted, and a plausible mechanism is proposed.
Catalytic Multisite-Selective Acetoxylation Reactions at sp2 vs sp3 C-H Bonds in Cyclic Olefins
Zang, Zhong-Lin,Zhao, Sheng,Karnakanti, Shuklachary,Liu, Cheng-Lin,Shao, Pan-Lin,He, Yun
supporting information, p. 5014 - 5017 (2016/10/14)
The first Pd-catalyzed multisite-selective acetoxylation reactions are disclosed at an unactivated alkene sp2 C-H bond versus secondary allylic sp3 C-H bond in cyclic olefins via the modulation of directing groups. The different directing groups overcome the key challenge in differentiating C-H bonds and provide a new controlling approach for site-specific C-H activation. A wide variety of substrates are readily acetoxylated under operationally simple conditions. Mechanistic studies suggest that different Pd (IV) intermediates were involved in the multisite-selective acetoxylation reactions.
Umpolung of Michael acceptors catalyzed by N-heterocyclic carbenes
Fischer, Christian,Smith, Sean W.,Powell, David A.,Fu, Gregory C.
, p. 1472 - 1473 (2007/10/03)
N-Heterocyclic carbenes can catalyze β-alkylations of a range of α,β-unsaturated esters, amides, and nitriles that bear pendant leaving groups to form a variety of ring sizes. In this process, the nucleophilic catalyst transiently transforms the normally electrophilic β carbon into a nucleophilic site through an unanticipated addition-tautomerization sequence. Copyright
Assembly of the 1-azaspiro[5.5]undecane framework associated with perhydrohistrionicotoxin via electrocyclic ring-opening of a ring-fused gem-dichlorocyclopropane and trapping of the resulting π-allyl cation by a tethered, nitrogen-centered nucleophile
Banwell, Martin G.,Vogt, Florian,Wu, Angela W.
, p. 415 - 425 (2007/10/03)
The carbamate-tethered gem-dichlorocyclopropane 27 was prepared, as a mixture of epimers, in ten steps from commercially available β,γ-unsaturated nitrile 9. Upon treatment with silver acetate under a range of reaction conditions, compound 27 underwent electrocyclic ring opening to give the corresponding ?-allyl cation that was then trapped by the reaction solvent, chloride ion, and/or acetate ion, and so affording varying mixtures of the chlorocyclohexenes 28, 29, 30, and/or 31. Sequential treatment of the same substrate with LiHMDS (to generate the conjugate base of this carbamate) then silver tetrafluoroborate afforded the chlorocyclohexadiene 32 as the exclusive product of reaction. No spirocyclization product of the type 3 arising from trapping of the intermediate ?-allyl cation by the tethered carbamate was observed under any of the reaction conditions examined. In contrast, analogous treatment of the more rigid system 38 afforded compound 39 incorporating the 1-azaspiro[5.5]undecane framework associated with the potent neurotoxin perhydrohistrionicotoxin (2). CSIRO 2006.
Addition of α-halo-substituted carbonitriles to and aldehydesketones in the presence of iron pentacarbonyl
Vasil'eva,Kuz'mina,Chakhovskaya,Mysova,Terent'ev
, p. 174 - 177 (2007/10/03)
Halo-substituted carbonitriles in the presence of iron pentacarbonyl react with aldehydes and ketones by Reformatsky reaction type. In contract to halo-substituted esters the nitriles are considerably more reactive toward ketones than aldehydes. At the same time the structure and yield of products obtained from both nitriles and esters are strongly and similarly affected by the character of the para-substituents in the benzaldehyde.
