- 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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- 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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- 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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- Design, synthesis and anticancer activity of functionalized spiro-quinolines with barbituric and thiobarbituric acids
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A new series of spiro-quinoline compounds have been accomplished by the reaction of barbituric acid or thiobarbituric acid with derivatives of benzisoxazole-5-carbaldehyde or 2-substituted benzaldehyde. These compounds were evaluated for their in vitro cy
- Bhaskarachar, Ravi Kiran,Revanasiddappa, Vijayakumar G.,Hegde, Subramanya,Balakrishna, Janardhana P.,Reddy, Suman Y.
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p. 3516 - 3528
(2015/08/03)
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- Aluminum complexes with bidentate amido ligands: Synthesis, structure and performance on ligand-initiated ring-opening polymerization of rac-lactide
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A series of mononuclear aluminum dimethyl complexes bearing bidentate N-[2-(1-piperidinyl)benzyl]anilino or N-(2-morpholinobenzyl)anilino ligands were synthesized via reactions of the corresponding proligands with trimethylaluminum upon heating, while at ambient temperature two trimethylaluminum adducts with neutral N-[2-(1-piperidinyl)benzyl]aniline proligands were obtained. These complexes were well characterized by NMR spectroscopy, elemental analysis and occasionally by EI-HRMS. The molecular structures of the typical trimethylaluminum adduct 2b and aluminum dimethyl complex 3b were further confirmed by X-ray diffraction studies. All the aluminum dimethyl complexes could effectively initiate the ring-opening polymerization (ROP) of rac-lactide in a well-controlled manner to afford PLAs with narrow molecular weight distributions (PDI = 1.06-1.18). The polymer samples obtained are systematically end-capped with the bidentate ancillary ligands as characterized by 1H NMR and ESI-TOF mass spectroscopy. Moreover, the introduction of substituent(s) at the ortho-position(s) of the anilino moiety in the ligand results in an obvious decrease in the catalytic activity of the corresponding aluminum complex, and complexes with meta-chloro substituted anilino units show higher activities likely due to the enhanced electrophilicity of the metal centers induced by the anilino groups. the Partner Organisations 2014.
- Liu, Junpeng,Ma, Haiyan
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p. 9098 - 9110
(2014/06/10)
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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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- Lewis acid catalyzed formation of 3-amino-3-carboxy-tetrahydroquinoline derivatives via tandem 1,5-hydride transfer/cyclization process
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A Sc(OTf)3-catalyzed intramolecular tandem 1,5-hydride transfer/cyclization process to construct 3-amino-3-carboxy-tetrahydroquinoline derivatives has been developed. The methodology gives access to a range of relatively complex tetrahydroquinolines (tetracyclic and pentacyclic heterocycles bearing spirocyclic skeleton and two stereogenic centers) in good to excellent yields with diastereoselectivities ranging from 57:43 to 73:27. The synthetic utility of the method was also demonstrated by an efficient ring opening derivatization reaction.
- Han, Wen-Yong,Zuo, Jian,Wu, Zhi-Jun,Zhang, Xiao-Mei,Yuan, Wei-Cheng
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p. 7019 - 7025
(2013/07/26)
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- HETEROCYCLYL PYRAZOLOPYRIMIDINE ANALOGUES AS JAK INHIBITORS
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The present invention relates to compounds of formula (I) wherein X1 to X5, Y, Z1 to Z3, and R have the meaning as cited in the description and the claims. Said compounds are useful as JAK inhibitors for the treatment or prophylaxis of immunological, inflammatory, autoimmune, allergic disorders, and immunologically-mediated diseases. The invention also relates to pharmaceutical compositions including said compounds, the preparation of such compounds as well as the use as medicaments.
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Page/Page column 160; 161
(2011/05/06)
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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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- Product-selectivity control by the nature of the catalyst: Lewis acid-catalyzed selective formation of ring-fused tetrahydroquinolines and tetrahydroazepines via intramolecular redox reaction
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Selective synthesis of ring-fused tetrahydroquinolines and tetrahydroazepines from the same starting materials was achieved by subtle use of the oxophilic Sc(OTf)3 or carbophilic IPrAuOTf as the catalyst.
- Zhou, Guanghua,Zhang, Junliang
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supporting information; scheme or table
p. 6593 - 6595
(2010/10/21)
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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 101
(2009/12/07)
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- RECEPTOR FUNCTION REGULATING AGENT
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An agent for regulating 14273 receptor function, which is useful as a preventing or treating drug for diabetes mellitus, hyperlipidemia or the like, is provided. An agent for regulating 14273 receptor function comprising a compound containing an aromatic ring and a group capable of releasing a cation.
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Page/Page column 86
(2010/11/23)
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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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