- Visible-Light Driven Selective C-N Bond Scission in anti-Bimane-Like Derivatives
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In the present study, we report the photochemical transformation of pyrazolo[1,2-a]pyrazolone substrates that reach an excited state upon irradiation with visible light to initiate the homolytic C-N bond cleavage process that yields the corresponding N1-s
- Petek, Nejc,Brodnik, Helena,Gro?elj, Uro?,Svete, Jurij,Po?gan, Franc,?tefane, Bogdan
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supporting information
p. 5294 - 5298
(2021/06/28)
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- Carbamoylation of Azomethine Imines via Visible-Light Photoredox Catalysis
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A versatile and robust photocatalytic methodology to install the amide functional group into azomethine imine ions is described. This protocol is distinguished by its broad scope and mild reaction conditions, which are well suited for the preparation of s
- Correia, José Tiago M.,Matsuo, Bianca T.,Oliveira, Pedro H. R.,Paix?o, Márcio W.
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supporting information
p. 6775 - 6779
(2021/09/13)
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- Facile and innovative catalytic protocol for intramolecular Friedel-Crafts cyclization of Morita-Baylis-Hillman adducts: Synergistic combination of chiral (salen)chromium(III)/ BF3 OEt2 catalysis
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The chiral (salen)Cr(III)/BF3 OEt2 catalytic combination was found to be an effective catalyst for intramolecular Friedel-Crafts cyclization of electron-deficient Morita-Baylis-Hillman adducts. In presence of mild reaction conditions the chiral (salen)Cr(
- Ayyanoth, Karthik Krishna Kumar,Jeyarajan, Helen Ratna Monica,Kamarajapurathu, Raju Subimol,Soundararajan, Karthikeyan
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supporting information
p. 2186 - 2193
(2021/09/02)
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- Visible-Light-Mediated α-Amino Alkylation of Azomethine Imines: An Approach to N-(β-Aminoalkyl)pyrazolidinones
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Herein, a mild and robust photocatalytic protocol for the combination of amino and pyrazolidinone functionalities through a radical α-amino alkylation of azomethine iminium ions is demonstrated. This method presents a high functional group tolerance provi
- Matsuo, Bianca T.,Correia, José Tiago M.,Paix?o, Márcio W.
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supporting information
p. 7891 - 7896
(2020/11/02)
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- Diversity Oriented Clicking (DOC): Divergent Synthesis of SuFExable Pharmacophores from 2-Substituted-Alkynyl-1-Sulfonyl Fluoride (SASF) Hubs
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Diversity Oriented Clicking (DOC) is a unified click-approach for the modular synthesis of lead-like structures through application of the wide family of click transformations. DOC evolved from the concept of achieving “diversity with ease”, by combining classic C?C π-bond click chemistry with recent developments in connective SuFEx-technologies. We showcase 2-Substituted-Alkynyl-1-Sulfonyl Fluorides (SASFs) as a new class of connective hub in concert with a diverse selection of click-cycloaddition processes. Through the selective DOC of SASFs with a range of dipoles and cyclic dienes, we report a diverse click-library of 173 unique functional molecules in minimal synthetic steps. The SuFExable library comprises 10 discrete heterocyclic core structures derived from 1,3- and 1,5-dipoles; while reaction with cyclic dienes yields several three-dimensional bicyclic Diels–Alder adducts. Growing the library to 278 discrete compounds through late-stage modification was made possible through SuFEx click derivatization of the pendant sulfonyl fluoride group in 96 well-plates—demonstrating the versatility of the DOC approach for the rapid synthesis of diverse functional structures. Screening for function against MRSA (USA300) revealed several lead hits with improved activity over methicillin.
- Barrow, Andrew S.,Cheng, Yunfei,Gialelis, Timothy L.,Giel, Marie-Claire,Kitamura, Seiya,Li, Gencheng,Moses, John E.,Ottonello, Alessandra,Sharpless, K. Barry,Smedley, Christopher J.,Wolan, Dennis W.
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supporting information
p. 12460 - 12469
(2020/06/10)
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- Br?nsted Acid-Catalyzed (4 + 3) Cyclization of N, N′-Cyclic Azomethine Imines with Isatoic Anhydrides
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A Br?nsted acid-catalyzed (4 + 3) cyclization of N,N′-cyclic azomethine imines with isatoic anhydrides has been discovered, which constructs seven-membered nitrogenous heterocyclic frameworks with overall high yields (up to 98% yield). This reaction repre
- Li, Can,Wang, Cong-Shuai,Li, Tian-Zhen,Mei, Guang-Jian,Shi, Feng
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supporting information
p. 598 - 602
(2019/01/25)
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- Photocatalytic reductive radical-radical coupling of: N, N ′-cyclicazomethine imines with difluorobromo derivatives
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A visible-light-induced difluoroalkylation of N,N′-cyclicazomethine imine was successfully realized through a novel photoredox radical-radical cross-coupling reaction. This developed protocol exhibits high functional group tolerance and affords a variety
- Xia, Peng-Ju,Ye, Zhi-Peng,Song, Dan,Ren, Ji-Wei,Wu, Han-Wen,Xiao, Jun-An,Xiang, Hao-Yue,Chen, Xiao-Qing,Yang, Hua
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supporting information
p. 2712 - 2715
(2019/03/05)
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- Solvent incorporated sequential [3 + 2] annulation/substitution reaction of azomethine imines and propargyl sulfur ylide
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A novel solvent incorporated sequential [3 + 2] cycloaddition/substitution reaction of azomethine imines with propargyl sulfur ylide was developed. In the actual three-component reaction, propargyl sulfur ylide acts as a dipole reagent to furnish the annu
- Shen, Shoujie,Yang, Yanli,Duan, Jiangyan,Jia, Zhenhu,Liang, Jinyan
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supporting information
p. 1068 - 1072
(2018/02/22)
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- Chiral Phosphine–Phosphite Ligands in Asymmetric Gold Catalysis: Highly Enantioselective Synthesis of Furo[3,4-d]-Tetrahydropyridazine Derivatives through [3+3]-Cycloaddition
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The AuI-catalyzed reaction of 2-(1-alkynyl)-2-alken-1-ones with azomethine imines regio- and diastereoselectively affords furo[3,4-d]tetrahydropyridazines in a tandem cyclization/intermolecular [3+3]-cycloaddition process under mild conditions.
- Du, Qingwei,Neud?rfl, J?rg-Martin,Schmalz, Hans-Günther
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supporting information
p. 2379 - 2383
(2018/01/27)
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- Asymmetric [3 + 2] Cycloaddition Employing N, N′-Cyclic Azomethine Imines Catalyzed by Chiral-at-Metal Rhodium Complex
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An efficient asymmetric 1,3-dipolar cycloaddition of α,β-unsaturated 2-acyl imidazoles with N,N′-cyclic azomethine imines catalyzed by a chiral-at-metal rhodium complex is reported. The corresponding N,N′-bicyclic pyrazolidine derivatives with three conti
- Gong, Jun,Wan, Qian,Kang, Qiang
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supporting information
p. 3354 - 3357
(2018/06/11)
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- Highly stereoselective [3+2]-cycloaddition reaction of stabilised N,N′-cyclic azomethine imines with 3-nitro-2-phenyl-2H-chromenes: Synthesis of tetrahydrochromeno[4,3-c]pyrazolo[1,2-a]pyrazol-11-ones
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The reactions of 3-nitro-2-phenyl-2H-chromenes with 2-arylmethylidene-5-oxopyrazolidin-2-ium-1-ides proceeded diastereoselectively to afford the corresponding tetrahydrochromeno[4,3-c]pyrazolo[1,2-a]pyrazol-11-ones in good yields as a result of the 1,3-dipolar cycloaddition reaction of stabilised N,N′-cyclic azomethine imines at the Δ3-bond of the chromene system.
- Barkov, Alexey Y.,Zimnitskiy, Nikolay S.,Kutyashev, Igor B.,Korotaev, Vladislav Y.,Sosnovskikh, Vyacheslav Y.
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p. 3989 - 3992
(2017/09/26)
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- Bronsted acid or lewis acid catalyzed [3+3] cycloaddition of azomethine imines with N-benzyl azomethine ylide: A facile access to bicyclic N-heterocycles
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1,3-Dipolar cycloaddition reactions are one of the most important methods to obtain diverse heterocycles with novel skeletons. We herein report the Bronsted acid or Lewis acid catalyzed [3+3] cycloaddition of azomethine imines with nonstabilized azomethine ylide generated in situ from an N-benzyl precursor, providing a clean and facile access to diverse bicyclic N-heterocycles in moderate to good yields for further biological testing. Also, the protocol developed achieved the formation of C-C and C-N bonds simultaneously in a single step.
- Li, Shuo-Ning,Yu, Bin,Liu, Jia,Li, Hong-Lian,Na, Risong
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supporting information
p. 282 - 286
(2016/01/20)
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- Diastereoselective 1,3-Dipolar Cycloadditions of N,N′-Cyclic Azomethine Imines with Iminooxindoles for Access to Oxindole Spiro-N,N-bicyclic Heterocycles
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In the presence of CuI, 1,3-dipolar cycloadditions of N,N′-cyclic azomethine imines with iminooxindoles proceeded readily and furnished novel oxindole spiro-N,N-bicyclic heterocycles in moderate to excellent chemical yields with excellent diastereoselecti
- Zhao, Hong-Wu,Li, Bo,Pang, Hai-Liang,Tian, Ting,Chen, Xiao-Qin,Song, Xiu-Qing,Meng, Wei,Yang, Zhao,Zhao, Yu-Di,Liu, Yue-Yang
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supporting information
p. 848 - 851
(2016/03/04)
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- [3 + 2]-Cycloadditions of Azomethine Imines and Ynolates
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A novel [3 + 2]-cycloaddition between azomethine imines and lithium ynolates is described to synthesize bicyclic pyrazolidinones. These bicyclic pyrazolidinones are versatile intermediates to form β-amino acids and monocyclic pyrazolidinones. High diaster
- Winterton, Sarah E.,Ready, Joseph M.
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supporting information
p. 2608 - 2611
(2016/06/15)
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- Asymmetric [3 + 2] Cycloaddition of Methyleneindolinones with N,N′-Cyclic Azomethine Imines Catalyzed by a N,N′-Dioxide-Mg(OTf)2 Complex
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A highly efficient chiral N,N′-dioxide-Mg(OTf)2 catalyst system has been developed for the asymmetric 1,3-dipolar cycloaddition between methyleneindolinones and N,N′-cyclic azomethine imines. The desired pyrazolidine products with contiguous qu
- Yin, Chengkai,Lin, Lili,Zhang, Dong,Feng, Juhua,Liu, Xiaohua,Feng, Xiaoming
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p. 9691 - 9699
(2015/10/12)
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- Chiral Iron(II) NPPN Complexes: Synthesis and Application in the Asymmetric Strecker Reaction of Azomethine Imines
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The open-chain NPPN ligand (1S,1′S)-1,1′-((ethane-1,2-diylbis(phenylphosphanediyl))bis(2,1-phenylene))bis(N-cyclohexylmethanimine) (1) was prepared by condensation of cyclohexylamine with enantiomerically pure (1S,1′S)-2,2′-(ethane-1,2-diylbis(phenylphosphanediyl))dibenzaldehyde ((S,S)-6). Ligand 1 coordinates to [Fe(OH2)6](BF4)2 or [Fe(MeCN)6](SbF6)2 in acetonitrile to give the dicationic complex [Fe(MeCN)2(1)](X)2 (2) (X = BF4- or SbF6-). The corresponding carbonyl (3), bromocarbonyl (4), and bis(tert-butylisonitrile) (5) derivatives were prepared and fully characterized. Complex 2 reacts with Me3SiCN to give the corresponding trimethylsilyl isocyanide derivative 18 featuring a Fe-CNSiMe3 linkage. The X-ray structures of 2, 3, 5, and 18 show that ligand 1 assumes the Λ-cis-α geometry, which allows comparing the trans influence of these ligands. Complexes 2, 3, 5, and 18 were applied in the asymmetric addition of trimethylsilyl cyanide to azomethine imines (Strecker reaction), whose enantioselectivity reached 22% ee. The low enantioselectivity can be explained on the basis of the Me3SiCN/Me3SiNC isomerization and of the reaction product partially displacing the NPPN ligand from iron.
- Huber, Raffael,Bigler, Raphael,Mezzetti, Antonio
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supporting information
p. 3374 - 3384
(2016/01/15)
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- Enantioselective 1,3-dipolar cycloaddition of azomethine imines with propioloylpyrazoles induced by chiral π-cation catalysts
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We developed 1,3-dipolar cycloadditions of azomethine imines with propioloylpyrazoles catalyzed by a chiral copper(II) complex of 3-(2-naphthyl)-L-alanine amide. The asymmetric environment created by intramolecular π - cation interaction and the N-alkyl group of the chiral ligand gives the corresponding adducts in high yields with excellent enantioselectivity. This is the first successful method for the catalytic enantioselective 1,3-dipolar cycloaddition of azomethine imines with internal alkyne derivatives to give fully substituted pyrazolines.
- Hori, Masahiro,Sakakura, Akira,Ishihara, Kazuaki
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supporting information
p. 13198 - 13201
(2015/03/30)
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- Phosphine-catalyzed [3+2] cycloaddition reactions of azomethine imines with electron-deficient alkenes: A facile access to dinitrogen-fused heterocycles
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An efficient method for the phosphine-catalyzed [3+2] cycloaddition reaction of azomethine imines with diphenylsulfonyl alkenes to give dinitrogen-fused bi- or tricyclic heterocyclic compounds in high yields has been described. Moreover, two phenylsulfony
- Li, Zhen,Yu, Hao,Liu, Honglei,Zhang, Lei,Jiang, Hui,Wang, Bo,Guo, Hongchao
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supporting information
p. 1731 - 1736
(2014/03/21)
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- Catalyst-free synthesis of N -(1,7-dioxotetrahydropyrazolo[1,2-a]pyrazol-2- yl)benzamide derivatives by 1,3-dipolar cycloaddition and rearrangement
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N-(1,7-Dioxotetrahydropyrazolo[1,2-a]pyrazol-2-yl)-benzamide derivatives, a novel class of compounds, were synthesized by 1,3-dipolar cycloaddition of azomethine imines with azlactones and subsequent rearrangement. The reaction can be completed rapidly under mild conditions without a catalyst. Georg Thieme Verlag Stuttgart New York.
- Liu, Wenjing,Xu, Yu,Sun, Xingxia,Lu, Dapeng,Guo, Lijuan
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supporting information
p. 1093 - 1096
(2014/05/20)
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- Nickel(ii)-catalyzed enantioselective 1,3-dipolar cycloaddition of azomethine imines with alkylidene malonates
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We demonstrated an asymmetric 1,3-dipolar cycloaddition of azomethine betaines with alkylidene malonates by using a chiral N,N'-dioxide- NiII complex as a catalyst. Both aromatic- and aliphatic-substituted alkylidene malonates were found to be suitable for the reaction. A range of transpyrazolone derivatives was exclusively obtained with excellent yields (up to 99% yield) and good enantioselectivities (up to 97% ee) under mild reaction conditions. The reaction could be carried out on a gram scale with the good results being maintained. Control experiments were performed to elucidate the specific diastereoselectivity of the reaction. The formation of single trans isomers was dominated by secondary orbital interactions between the ester groups of the dipolarophile and the azomethine imine. On the basis of the experimental results and previous reports, a possible catalytic model was assumed.
- Li, Jiangting,Lian, Xiangjin,Liu, Xiaohua,Lin, Lili,Feng, Xiaoming
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supporting information
p. 5134 - 5140
(2013/07/05)
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- Enantioselective copper-catalyzed [3+3] cycloaddition of azomethine ylides with azomethine imines
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The more dipoles, the merrier: An asymmetric [3+3] cycloaddition of azomethine ylides derived from imines 1 with azomethine imines 2 in the presence of a chiral ferrocenylphosphine-copper catalyst afforded highly functionalized heterocyclic products 3 in high yield with excellent enantio- and diastereoselectivity (see scheme; DBU=1,8-diazabicyclo[5.4.0]undec-7-ene). The 1,3-dipolar reaction partners can be readily prepared from aldehydes. Copyright
- Guo, Hongchao,Liu, Honglei,Zhu, Fu-Lin,Na, Risong,Jiang, Hui,Wu, Yang,Zhang, Lei,Li, Zhen,Yu, Hao,Wang, Bo,Xiao, Yumei,Hu, Xiang-Ping,Wang, Min
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supporting information
p. 12641 - 12645
(2013/12/04)
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- Copper(I) acetate-catalyzed cycloaddition between azomethine imines and propiolates under additive-free conditions
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Because propiolates easily undergo base-catalyzed self-Michael addition, most popular catalytic systems in CuAAC cannot be used in the cycloaddition between azomethine imines and propiolates, because such reactions usually require the use of tertiary amin
- Shao, Changwei,Zhang, Qun,Cheng, Guolin,Cheng, Chuanjie,Wang, Xinyan,Hu, Yuefei
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p. 6443 - 6448
(2013/10/21)
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- Dirhodium(ii)-catalyzed formal [3+2+1]-annulation of azomethine imines with two molecules of a diazo ketone
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A highly diastereoselective formal [3+2+1]-cycloaddition reaction that produces multi-functionalized bicyclic pyrazolidinone derivatives is achieved in moderate to high yield by Rh2(4S-MPPIM)4-catalyzed reaction of azomethine imines with two molecules of a diazo ketone. The Royal Society of Chemistry 2013.
- Xu, Xinfang,Xu, Xichen,Zavalij, Peter Y.,Doyle, Michael P.
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supporting information
p. 2762 - 2764
(2013/04/23)
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- Catalyst free 1,3-dipolar cycloaddition of 3-oxo-1,2-pyrazolidinium ylides to β-trifluoroacetyl vinyl ethyl ether: Synthesis of 6-trifluoroacetyl substituted bicyclic pyrazolidinones
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A catalyst free cycloaddition reaction of 3-oxo-1,2-pyrazolidinium ylides with β-trifluoroacetyl vinyl ethyl ether is reported, which proceeded smoothly at ambient temperature and afford the bicyclic pyrazolidinone products in good yield. This is the firs
- Xin, Yong,Zhao, Jingwei,Gu, Jiwei,Zhu, Shizheng
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experimental part
p. 402 - 408
(2011/07/30)
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- Copper(I) zeolites as heterogeneous and ligand-free catalysts: [3+2] cycloaddition of azomethine imines
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Copper(I)-exchanged zeolites were used as heterogeneous ligand-free catalysts for [3+2] cycloaddition of azomethine ylides, which allows versatile, efficient, and highly regioselective synthesis of pyrazolone derivatives. These cheap and easy-to-prepare c
- Keller, Murielle,Sani Sido Souna, Abdelkarim,Pale, Patrick,Sommer, Jean
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supporting information; experimental part
p. 2810 - 2817
(2009/12/04)
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- Copper(II)-catalyzed exo and enantioselective cycloadditions of azomethine imines
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(Chemical Equation Presented) A strategy for exo and enantioselective 1,3-dipolar cycloaddition of azomethine imines to 2-acryloyl-3-pyrazolidinone is described. The corresponding cycloadducts are isolated with high diastereoselectivities (up to > 96:4 ex
- Sibi, Mukund P.,Rane, Digamber,Stanley, Levi M.,Soeta, Takahiro
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supporting information; experimental part
p. 2971 - 2974
(2009/05/11)
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- A new copper-catalyzed [3 + 2] cycloaddition: Enantioselective coupling of terminal alkynes with azomethine imines to generate five-membered nitrogen heterocycles
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A copper-catalyzed method for the regioselective 1,3-dipolar cycloaddition of azomethine imines to terminal alkynes has been developed. Through the use of a chiral phosphaferrocene-oxazoline ligand, a wide range of substrates can be coupled to generate us
- Shintani, Ryo,Fu, Gregory C.
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p. 10778 - 10779
(2007/10/03)
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- Azomethineimine. VI. On the Thermic Behaviour of the Photochromic System Azomethineimine/Diaziridine, Investigated by Means of the Photoproducts of Pyrazolidone-(3)-Azomethineimines
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The photochemically obtained cycloproducts 2 of pyrazolidone-(3)-azomethineimines 1 react thermically to 1 in aprotic solvents.This backreaction was investigated by following up the growth of the intensive long wave absorption band of 1.The kinetic analysis was carried out according to Swinbourne.The thermic backreaction is accelerated by factors favouring a polarization of the C-N(2)-bond (Cδ+ - Nδ-) of diaziridine 2.Such factors are polar solvents, donors in the substituent R and extensive, easily polarizable ?-electronic systems in R.The influence of substituents on the backreaction can be correlated by means of the ?+-Hammett-constants.For most compounds the values of EA ca. ΔH(excit.),ΔS(excit.) and ΔG(excit.) were determined.The possible reaction mechanism is discussed.The influence of steric factors on the thermic backreaction is regarded as a first indication of an exo-form of the bicyclic diaziridines 2.
- Geissler, G.,Menz, I.,Angermueller, K.,Tomaschewski, G.
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p. 197 - 204
(2007/10/02)
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- Synthesis and properties of 3-oxo-1,2-diazetidinium ylides
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Treatment of α-chloroacylhydrazones of diaryl and certain aralkyl and dialkyl ketones with sodium hydride in anhydrous tetrahydrofuran gives 1-(disubstituted methylene)-3-oxo-1,2-diazetidinium inner salts (ylides). The reaction pathway involves formation of the hydrazone anion followed by intramolecular SN2 halide displacement (with complete inversion at the α carbon) by the sp2 imine nitrogen. These 1-(disubstituted methylene)-3-oxo-1,2-diazetidinium ylides are reduced by sodium borohydride to give 1-substituted 1,2-diazetidin-3-ones, undergo dipolar cycloaddition reactions to give fused aza-β-lactams, and can be hydrolyzed with p-toluenesulfonic acid monohydrate to the p-toluenesulfonic acid salt of 1,2-diazetidinone.
- Taylor, Edward C.,Haley, Neil F.,Clemens, Robert J.
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p. 7743 - 7752
(2007/12/18)
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- Azomethine-Imines. I. To the Photoreversibility of the System Azomethine-Imine/Diaziridine, Investigated on Pyrazolidone-Azomethine-Imines.
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Pyrazolidone-azomethine-Imines of the type 1 with polycyclic aromatic substituents R undergo a photoreversible reaction to diaziridines 2.In the u.v./VIS-spectra of the two forms 1 and 2 the difference of the λmax-values is about 100 nm.Therefore this system is suitable as a new reversible photochromic system.The influence of substituents R' to the u.v./VIS-spectra of the 1.3-dipolar form 1 is discussed.
- Tomaschewski, G.,Geissler, G.,Schauer, G.
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p. 623 - 628
(2007/10/02)
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