- HPLC-ECD and TDDFT-ECD study of hexahydropyrrolo[1,2-a]quinoline derivatives
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Synthesis of racemic hexahydropyrrolo[1,2-a]quinoline derivatives (1-8) was performed by utilizing the Knoevenagel-[1,5]-hydride shift-cyclization domino reaction. Separation of the enantiomers of the chiral products (1-8) was carried out by chiral high-p
- Tóth, László,Mándi, Attila,Váradi, Dániel,Kovács, Tibor,Szabados, Anna,Kiss-Szikszai, Attila,Gong, Qi,Zhang, Haiyan,Mátyus, Péter,Antus, Sándor,Kurtán, Tibor
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Read Online
- Well-controlled ring-opening polymerization of cyclic esters catalyzed by aluminum amido complexes: Kinetics and mechanism
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A series of aluminum dimethyl complexes 1-6 bearing N-[2-(pyrrolidinyl)benzyl]anilido ligands were synthesized and well characterized. The molecular structure of complex 1 determined by an X-ray diffraction study indicates the bidentate chelating mode of
- Liu, Junpeng,Ma, Haiyan
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Read Online
- Double Capture of Difluorocarbene by 2-Aminostyrenes Enables the Construction of 3-(2,2-Difluoroethyl)-2-fluoroindoles
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We report herein an efficient strategy to construct 3-(2,2-difluoroethyl)-2-fluoroindoles from activated o-aminostyrenes with ethyl bromodi-fluoroacetate as a difluorocarbene source. Through double capture of a difluorocarbene, two different types of fluo
- Sheng, Heyun,Su, Jianke,Li, Xin,Li, Xue,Song, Qiuling
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supporting information
p. 7781 - 7786
(2021/10/25)
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- Hexafluoroisopropanol-Mediated Redox-Neutral α-C(sp3)-H Functionalization of Cyclic Amines via Hydride Transfer
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Hexafluoroisopropanol has been demonstrated as the versatile promoter for redox-neutral α-C(sp3)-H functionalization of cyclic amines via the cascade [1,5]-hydride transfer/cyclization strategy. A wide range of cyclic amines are functionalized
- Shen, Yao-Bin,Wang, Lin-Xuan,Sun, Yun-Ming,Dong, Feng-Ying,Yu, Liping,Liu, Qing,Xiao, Jian
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p. 1915 - 1926
(2020/02/04)
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- Development of TsDPEN based imine-containing ligands for the copper-catalysed asymmetric Kinugasa reaction
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A novel class of chiralN,N,Nimine-containing ligands derived from TsDPEN (N-(p-tosyl)-1,2-diphenylethylene-1,2-diamine) has been developed and applied to the copper-catalyzed asymmetric Kinugasa reaction. The copper(ii) salt proved to be an efficient catalyst precursor, and it provides an efficient way to synthesize enantioenrichedcis-β-lactam. The pathway is air-tolerant and easily manipulated, and the ligands are easy to synthesize. A working model is proposed in which the stereocontrolling step is the [2 + 2] cycloaddition between ketene and imine to explain the observed stereoselectivities.
- Deng, Ping,He, Feilong,He, Huakang,Wu, Yue,Xu, Chuanlong,Yang, Yuchen,Zhou, Hui
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p. 18107 - 18114
(2020/06/08)
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- Catalyst-free photodecarbonylation ofortho-amino benzaldehyde
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It is almost a consensus that decarbonylation of the aldehyde group (-CHO) needs to not only be mediated by transition metal catalysts, but also requires severe reaction conditions (high temperature and long reaction time). In this work, inspired by the “conformational-selectivity-based” design strategy, we broke this consensus and discovered a catalyst-free photodecarbonylation of the aldehyde group. It revealed that decarbonylation can be easily achieved with visible light irradiation by introducing a tertiary amine into theortho-position of the aldehyde group. A diverse array of tertiary amines is tolerated by our photodecarbonylation under mild conditions. Furthermore, the (QM) computations of the mechanism and the experiments on well-designed special substrates revealed that our photodecarbonylation depends on the conformational specificity of the aldehyde group and tertiary amine, and occurs through an unusual [1,4]-H shift and a subsequent [1,3]-H shift.
- Li, Lamei,Wang, Songping,Wei, Wentao,Yan, Ming,Zhou, Jingwei
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supporting information
p. 3421 - 3426
(2020/06/25)
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- 4-(2-(pyrrolidine/piperidine-1-yl)benzyl)-piperazine urea TRPV1 antagonist and preparation method and application thereof
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The invention discloses a novel 4-(2-(pyrrolidine/piperidine-1-yl)benzyl)-piperazine urea type TRPV1 antagonist and a preparation method and application thereof. The invention relates to a compound ina general formula (I) and a pharmaceutically acceptable
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Paragraph 0059-0062
(2020/08/06)
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- Redox-Neutral Cascade Dearomatization of Indoles via Hydride Transfer: Divergent Synthesis of Tetrahydroquinoline-Fused Spiroindolenines
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The redox-neutral cascade dearomatization of indoles with o-aminobenzaldehydes has been realized via the hydride transfer strategy, achieving the condition- A nd substrate-controlled divergent synthesis of tetrahydroquinoline-fused spiroindolenines. The integration of hydride transfer-involved C(sp3)-H functionalization with dearomatization provides a promising platform for the construction of structurally diverse molecules.
- Shen, Yao-Bin,Li, Long-Fei,Xiao, Ming-Yan,Yang, Jian-Ming,Liu, Qing,Xiao, Jian
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p. 13935 - 13947
(2019/11/11)
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- N-Alkylation-Initiated Redox-Neutral [5 + 2] Annulation of 3-Alkylindoles with o-Aminobenzaldehydes: Access to Indole-1,2-Fused 1,4-Benzodiazepines
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Described herein is an unprecedented N-Alkylation-initiated redox-neutral [5 + 2] annulation of 3-Alkylindoles with o-Aminobenzaldehydes via a cascade N-Alkylation/dehydration/[1,5]-hydride transfer/Friedel-Crafts alkylation sequence. A series of indole-1,2-fused 1,4-benzodiazepines are facilely constructed in moderate to good yields in one step. This protocol features excellent regioselectivity, metal-free conditions, high step economy, and wide substrate scope.
- Wang, Shuai,Shen, Yao-Bin,Li, Long-Fei,Qiu, Bin,Yu, Liping,Liu, Qing,Xiao, Jian
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supporting information
p. 8904 - 8908
(2019/11/19)
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- Spirocyclic Tetramates by Sequential Knoevenagel and [1,5]-Prototropic Shift
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Highly functionalized spirocyclic tetramates were prepared via a sequential Knoevenagel reaction and [1,5]-prototropic shift (T-reaction) of bicyclic tetramates. While these compounds isomerize in solution, stable analogues can be prepared via an appropri
- Josa-Culleré, Laia,Hirst, Michael G.,Lockett, Jonathan P.,Thompson, Amber L.,Moloney, Mark G.
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p. 9671 - 9683
(2019/09/06)
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- Tetrahydroquinazoline derivatives and synthesis method and applications thereof
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The invention provides tetrahydroquinazoline derivatives and a synthesis method and applications thereof. The synthesis method is characterized by comprising following steps: carrying out aromatic ring nucleophilic substitution reactions between substitut
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Paragraph 0065-0069; 0078-0082; 0091-0095
(2019/05/08)
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- BF3·OEt2-Promoted Propargyl Alcohol Rearrangement/[1,5]-Hydride Transfer/Cyclization Cascade Affording Tetrahydroquinolines
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An efficient BF3·OEt2-mediated propargyl alcohol rearrangement/[1,5]-hydride transfer/cyclization cascade for the synthesis of tetrahydroquinoline derivatives has been described. The substituents adjacent to triple bonds play an important role in the formation of ketones (via [1,3]-hydroxyl shift) or alkenyl fluorides which are products of formal trans-carbofluorination of internal alkynes. This method provides a rapid access to diverse heterocycles in moderate to excellent yields.
- Zhao, Shuang,Wang, Xiaoyang,Wang, Pengfei,Wang, Guangwei,Zhao, Wentao,Tang, Xiangyang,Guo, Minjie
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supporting information
p. 3990 - 3993
(2019/06/14)
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- Investigation of the [1,5]-hydride shift as a route to nitro-Mannich cyclisations
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Conditions were found for the [1,5]-hydride shift nitro-Mannich reaction that led to the synthesis of 2,3-disubstituted tetrahydroquinolines. Two simple cyclic amine substrates gave diastereomerically pure rearranged products in 65 and 90% yields by refluxing in HFIP. A more general procedure used Gd(OTf)3 as a catalyst and successfully rearranged other cyclic and acyclic amines in 42–84% yield with diastereomeric ratios of 75:25 to >95:5 in favour of the anti-diastereoisomer (9 examples). Two examples of sulphur containing heterocycles gave lower yields of 9 and 25%. Electron withdrawing substituents were shown to have a deleterious effect on the success of the reaction. The results indicated the limitation of the [1,5]-hydride shift nitro-Mannich reaction with respect to the stability of the intermediate iminium ion.
- Anderson, James C.,Chang, Chia-Hao,Corpinot, Mérina K.,Nunn, Michael,Ware, Oliver J.
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- Direct Intermolecular C-H Functionalization Triggered by 1,5-Hydride Shift: Access to N-Arylprolinamides via Ugi-Type Reaction
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A novel Ugi-type reaction triggered by 1,5-hydride shift has been established, giving access to N-arylprolinamides and related compounds in high atom economy and good yields. This is an example of a two starting material-three component reaction. The benz
- Zhen, Le,Wang, Jiankun,Xu, Qing-Long,Sun, Hongbin,Wen, Xiaoan,Wang, Guangji
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supporting information
p. 1566 - 1569
(2017/04/13)
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- Diastereo- and Enantioselective Assembly of Spirooxindole Tetrahydroquinoline Skeletons through Asymmetric Binary Acid Catalyzed Hydride Transfer-Cyclization
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An efficient binary acid catalyzed asymmetric intramolecular tandem 1,5-hydride transfer/ring-closure reaction was achieved. The process is catalyzed by the combination of a chiral spirocyclic phosphoric acid and magnesium chloride to afford structurally diverse spirooxindole tetrahydroquinolines in good yields with high diastereo- and enantioselectivities.
- Mao, Zhenjun,Mo, Fan,Lin, Xufeng
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supporting information
p. 546 - 550
(2016/03/12)
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- Asymmetric Pentafulvene Carbometalation - Access to Enantiopure Titanocene Dichlorides of Biological Relevance
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Unprecedented asymmetric copper-catalyzed addition of ZnEt2 (ZnBu2) to the exocyclic C=C bond of pentafulvenes C5H4(=CHAr) (Ar=2-MeOPh and related species) results in enantiomerically enriched (up to 93:7 e.r.)
- Cini, Melchior,Bradshaw, Tracey D.,Woodward, Simon,Lewis, William
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supporting information
p. 14179 - 14182
(2016/01/25)
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- Asymmetric tandem 1,5-hydride shift/ring closure for the synthesis of chiral spirooxindole tetrahydroquinolines
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The direct functionalization of sp3 C-H bonds through a tandem 1,5-hydride shift/ring closure is described. Various optically active spirooxindole tetrahydroquinoline derivatives bearing contiguous quaternary or tertiary stereogenic carbon centers were readily synthesized. A chiral scandium complex of N,N'-dioxide promoted the reactions in good yields (up to 97%) with excellent diastereoselectivities (>20:1) and enantioselectivities (up to 94% ee). Kinetic isotope effect (KIE) experiments and internal redox reactions of chiral substrates were conducted, and the results provided intriguing information that helped clarify the mechanism of the reaction.
- Cao, Weidi,Liu, Xiaohua,Guo, Jing,Lin, Lili,Feng, Xiaoming
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supporting information
p. 1632 - 1636
(2015/01/30)
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- Chemo-, Regio-, and stereoselective trifluoromethylation of styrenes via visible light-driven single-electron transfer (SET) and triplet-triplet energy transfer (TTET) processes
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A process for tunable and chemo-, regio-, and stereoselective photocatalytic trifluoromethylation of styrenes was developed. Thermodynamically stable E-trifluoromethylated alkenes were prepared using Tognis reagent in the presence of Ru(bpy)3Cl2·6H2O under visible light irradiation, whereas less thermodynamically stable Z-trifluoromethylated alkenes were obtained by employing Umemotos reagent and photocatalyst Ir(ppy)3.
- Lin, Qing-Yu,Xu, Xiu-Hua,Qing, Feng-Ling
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p. 10434 - 10446
(2015/02/19)
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- IMIDAZOTRIAZINONE COMPOUNDS
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The present invention provides imidazotriazinone compounds which are inhibitors of phosphodiesterase 9 and pharmaceutically acceptable salt thereof. The present invention further provides processes, pharmaceutical compositions, pharmaceutical preparations and pharmaceutical use of the compounds in the treatment of PDE9 associated diseases or disorders in mammals, including humans.
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Paragraph 0739; 0740; 0741
(2013/10/08)
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- 2-aminobenzaldehydes as versatile substrates for rhodium-catalyzed alkyne hydroacylation: Application to dihydroquinolone synthesis
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Amine for it! A cationic rhodium catalyst, which was assembled insitu from commercial components, promoted the reaction of a range of simple 2-aminobenzaldehydes with terminal and internal alkynes in a series of intermolecular hydroacylation reactions. The products of this reaction, amino-substituted enones, were efficiently converted into the corresponding dihydro-4-quinolones.
- Castaing, Matthias,Wason, Sacha L.,Estepa, Beatriz,Hooper, Joel F.,Willis, Michael C.
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supporting information
p. 13280 - 13283
(2014/01/06)
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- FeCl3-catalyzed stereoselective construction of spirooxindole tetrahydroquinolines via tandem 1,5-hydride transfer/ring closure
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An efficient FeCl3-catalyzed stereoselective intramolecular tandem 1,5-hydride transfer/ring closure reaction was developed. The method allows for the formation of structurally diverse spirooxindole tetrahydroquinolines in high yields (up to 98%) with good to excellent levels of diastereoselectivity (up to 99:1 dr). The catalytic enantioselective variant of this process was also investigated preliminarily with a chiral BINOL-derived phosphoric acid.
- Han, Yan-Yan,Han, Wen-Yong,Hou, Xue,Zhang, Xiao-Mei,Yuan, Wei-Cheng
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supporting information; scheme or table
p. 4054 - 4057
(2012/09/21)
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- Synthesis of fused indazole ring systems and application to nigeglanine hydrobromide
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The single-step synthesis of fused tricyclic pyridazino[1,2-a]indazolium ring systems is described. Structural details revealed by crystallography explain the unexpected reactivity. The method is applied to the gram scale synthesis of nigeglanine hydrobro
- Sather, Aaron C.,Berryman, Orion B.,Rebek, Julius
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supporting information; experimental part
p. 1600 - 1603
(2012/06/05)
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- Intramolecular redox-triggered C-H functionalization
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Sacrifice for the team: A one-pot method achieves remote functionalization at the α-position of an amine moiety through the sacrificial reduction of a neighboring group. The process takes advantage of an intramolecular redox reaction, thereby avoiding the need for any external oxidants. This method was applied to a concise five-step total synthesis of indolizidine 167B.
- Jurberg, Igor D.,Peng, Bo,Woestefeld, Eckhard,Wasserloos, Maximilian,Maulide, Nuno
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supporting information; experimental part
p. 1950 - 1953
(2012/04/04)
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- Studies on electronic effects in O-, N- and S-chelated ruthenium olefin-metathesis catalysts
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A short overview on the structural design of the Hoveyda-Grubbs-type ruthenium initiators chelated through oxygen, nitrogen or sulfur atoms is presented. Our aim was to compare and contrast O-, N- and S-chelated ruthenium complexes to better understand the impact of electron-withdrawing and -donating substituents on the geometry and activity of the ruthenium complexes and to gain further insight into the trans-cis isomerisation process of the S-chelated complexes. To evaluate the different effects of chelating heteroatoms and to probe electronic effects on sulfur- and nitrogen-chelated latent catalysts, we synthesised a series of novel complexes. These catalysts were compared against two well-known oxygen-chelated initiators and a sulfoxide-chelated complex. The structures of the new complexes have been determined by single-crystal X-ray diffraction and analysed to search for correlations between the structural features and activity. The replacement of the oxygen-chelating atom by a sulfur or nitrogen atom resulted in catalysts that were inert at room temperature for typical ring-closing metathesis (RCM) and cross-metathesis reactions and showed catalytic activity only at higher temperatures. Furthermore, one nitrogen-chelated initiator demonstrated thermo-switchable behaviour in RCM reactions, similar to its sulfur-chelated counterparts.
- Tzur, Eyal,Szadkowska, Anna,Ben-Asuly, Amos,Makal, Anna,Goldberg, Israel,Wozniak, Krzysztof,Grela, Karol,Lemcoff, N. Gabriel
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experimental part
p. 8726 - 8737
(2010/10/19)
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- Novel, versatile three-step synthesis of 1,2,3,4,10,10a-hexahydro- pyrazino[1,2- a ]indoles by intramolecular carbene-mediated C-H insertion
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A new convenient three-step synthesis of the privileged CNS scaffold 1,2,3,4,10,10a-hexahydropyrazino[1,2-a]indoles has been developed. The method makes use of an intramolecular carbene-mediated C-H insertion in phenylpiperazine-derived tosyl-hydrazones m
- Krogsgaard-Larsen, Niels,Begtrup, Mikael,Herth, Matthias M.,Kehler, Jan
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experimental part
p. 4287 - 4299
(2011/02/22)
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- NOVEL CURCUMIN DERIVATIVE
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The present invention provides a novel compound that is structurally similar to curcumin and has a suppressive effect on Aβ aggregation, a degradative effect on Aβ aggregates, an inhibitory effect on β-secretase, and a protective effect on neurons. The novel compound is a compound represented by the following general formula (Ia) or a salt thereof: wherein R1 represents a 4-hydroxy-3-methoxyphenyl group or the like, and R2 represents a 1H-indol-6-yl group or the like.
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Page/Page column 100
(2009/12/07)
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- Scope and limitations of the T-reaction employing some functionalized C-H-acids and naturally occurring secondary amines
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Scope and limitations of the T-reaction with emphasis on using chiral, natural products as starting materials to prepare novel chiral heterocycles is studied and the diastereoselective introduction of newly formed stereocenters is explained via proposed mechanisms.
- Rabong, Constantin,Hametner, Christian,Mereiter, Kurt,Kartsev, Victor G.,Jordis, Ulrich
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p. 799 - 838
(2008/09/21)
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- PYRROLOPYRIMIDINE DERIVATIVES USEFUL AS MODULATORS OF MULTIDRUG RESISTANCE
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A compound which is a pyrrolopyrimidine of formula (I) wherein: R1 is selected from R9 and halogen; R2 is NR6R7; R3 is selected from H, C1-C6 alkyl which is unsubstituted or substituted and -(CH2) nAr; R4 is selected from H, C1-C6 alkyl and -(CH2)? Ar; or R3 and R4 form, together with the N and C atoms to which they are attached, a fused five-, six-, seven- or eight-membered N-containing saturated ring which is unsubstituted or substituted; R5 is selected from CN, C02R9,C(O)NR10R11, -(CH2)nOH, -(CH2)nR10Rn, -C=CH, -C(S)NR10R11, -C(NH2)=NOR9, -C(R9)=NOR9, -C(NH2)NH, -C(O)R9 and an unsaturated 5- or 6-membered heterocyclic group which contains 1, 2 or 3 heteroatoms selected from N, O and S and which is unsubstituted or substituted; R6 and R7, which are the same or different, are selected from C1-C6 alkyl which is unsubstituted or substituted, -(CH2)nX and -(CH2)nAr; or R6 and R7 form, together with the nitrogen atom to which they are attached, a saturated five-, six-, seven- or eight-membered heterocyclic group which contains one nitrogen atom and 0 or from 1 to 3 additional heteroatoms selected from N, O and S, which is unsubstituted or substituted and which optionally contains one or two bridgehead atoms; R10and R11,which are the same or different, are selected from H, C1-C6 alkyl which is unsubstituted or substituted, -(CH2)nC3-C10 cycloalkyl and -(CH2)nAr; or R10 and R11 form, together with the nitrogen atom to which they are attached, a saturated five or six membered heterocyclic group which contains a nitrogen atom and 0 or from to 3 additional heteroatoms selected from O, S and N, which is unsubstituted or substituted and which is optionally fused to a benzene ring which is unsubstituted or substituted; n is the same or different when more than one is present within a given substituent group and is 0 or an integer of from 1 to 6; X is selected from -CN, -C02R9 and -NR10R11; R9 is the same or different when more than one is present within a given substituent group and is selected from -H, -QAr, -(CH2) nAr, C1-C6 alkyl which is unsubstituted or substituted and -(CH2) nC3-C10cycloalkyl, wherein the cycloalkyl moiety is optionally fused to a benzene ring which is unsubstituted or substituted; Q is C2-C6 alkenylene or alkynylene; and Ar is an unsaturated C6-C10 membered carbocyclic group or an unsaturated 5-11 membered heterocyclic group, which groups are unsubstituted or substituted; or a pharmaceutically acceptable salt thereof. These compounds have activity as inhibitors of MRP (multidrug resistant protein) and may thus be used to modulate multidrug resistance, for instance in potentiating the cytotoxicity of a chemotherapeutic agent.
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- tert-Amino effect in heterocyclic chemistry. Synthesis of hydrogenated spiro derivatives of quinolines
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A new method was developed for the one-step synthesis of spiro derivatives of fused quinolines by the reactions of ortho-amino derivatives of benzaldehyde with Meldrum's acid, cyclohexane-1,3-dione, or N,N′-disubstituted barbituric acids.
- D'yachenko,Glukhareva,Nikolaenko,Tkachev,Morzherin
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p. 1240 - 1247
(2007/10/03)
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- Tandem radical cyclisation and translocation approaches to biologically important mitomycin ring systems
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New free-radical cyclisation and translocation approaches to the tricyclic mitomycin ring system have been developed. These convergent approaches involve either a tandem 5-endo/5-exo radical cyclisation or alternatively, a 1,6-hydrogen-atom transfer follo
- Allan, Gillian M.,Parsons, Andrew F.,Pons, Jean-Fran?ois
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p. 1431 - 1434
(2007/10/03)
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