- Two unprecedented aromatic guanidines supramolecular chains self-assembled by hydrogen bonding interaction
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Two aromatic guanidine derivatives, C6H5N = C(NHCy)2 (1), (n-TBA)C6H5NHC(NHCy)2Mo2O7 (2) (Cy = cyclohexyl), were synthetized with high yields. Both of them self-assemb
- Zhang, Yunshen,Huang, Yichao,Zhang, Jiangwei,Zhu, Li,Chen, Kun,Hao, Jian
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- L-Cysteine capped Zn nanoparticles catalyzed synthesis of guanidines
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A highly chemoselective method for the coupling of carbodiimides with primary amines to synthesize guanidines is achieved using L-cysteine capped zinc nanoparticles (NPs) as a catalyst. The efficiency of the catalyst is proved by recyclability and reusability studies. Surface characterization of the catalyst before and after its repetitive usage proved the stability of the catalyst.
- Muthuvinothini, Alagesan,Stella, Selvaraj
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- Nanoparticulate copper(II) oxide catalyzed synthesis of guanidine derivatives and their conversion into functionalized iminoguanidines
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Abstract A simple synthesis of functionalized iminoguanidines from N-sulfoketenimines and N,N′,N′′-trisubstituted guanidines, generated by nanoparticulate copper(II) oxide-catalyzed hydroamination of di(cyclo)alkylcarbodiimides, is described.
- Yavari, Issa,Sodagar, Esmat,Nematpour, Manijeh,Askarian-Amiri, Mohammad
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- Five-coordination aluminum complexes: Synthesis, crystal structures and utilization for the construction of substituted guanidines
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Insertion of 2,6-iPr2C6H3N(Li)SiMe3 or PhN(Li)SiMe3 to the CN bond of Me2NCN or PhCN afforded the lithium complexes [Li(2,6-iPr2C6H3)NC(NMe2)NC(NMe2)N(SiMe3)]2 (1a) and [Li(PhNC(Ph)NSiMe3)]2 (1b). Complexes 1a and 1b were used as precursors to react with AlCl3 affording [(2,6-iPr2C6H3)NC(NMe2)NC(NMe2)N(SiMe3)]2AlCl (2) and [(PhNC(Ph)NSiMe3)]2AlCl (3), respectively. The structures of 2 and 3 were presented. Both 2 and 3 exhibit good activity to catalyze the addition reaction of arylamines to N,N'-diisopropylcarbodiimide.
- Song, Qiuhong,Tong, Hongbo,Zhou, Meisu
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- Combination of air/moisture/ambient temperature compatible organolithium chemistry with sustainable solvents: Selective and efficient synthesis of guanidines and amidines
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Highly-efficient and selective fast addition of in situ generated lithium amides [LiN(H)R] (obtained via an acid-base reaction between n-BuLi and the desired primary amine) into carbodiimides (R-NCN-R) or nitriles (R-CN) has been studied, for the first ti
- Anti?olo, Antonio,Carrillo-Hermosilla, Fernando,Elorriaga, David,García-álvarez, Joaquín,Parra-Cadenas, Blanca
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supporting information
p. 800 - 812
(2022/02/02)
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- Synthesis, structure and catalytic activity of rare-earth metal amino complexes incorporating imino-functionalized indolyl ligand
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The reactions of the imino-functionalized indolyl ligand (HL, L = 3-(4-Me2N-C6H4CH=N-CH2CH2)C8H5N) with the rare-earth metal amides [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 producing different types of rare-earth metal amido complexes were investigated. The reactions of HL with 1 equiv. of [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 generated a series of hetero-nuclear bimetallic rare-earth metal amino complexes {[η1:μ-η2-3-(4-Me2N-C6H4CH=N-CH2CH2)C8H5]RE[N(SiMe3)2]2(μ-Cl)Li(THF)} (RE = Y(1), Sm(2), Gd(3), Er(4), Yb(5)). By extending the reaction time, only the reaction of HL with [(Me3Si)2N]3Gd(μ-Cl)Li(THF)3 gave an unexpected binuclear rare-earth metal complex {[(μ-η5:η1):η1:η1-3-[(Me2N)2-C14H9]-(NCH2CH2-C8H5N)2]Gd2[N(SiMe3)2]3} (6) incorporating a novel polycyclic ligand through C-C and C-N coupling. Treatment of HL with [(Me3Si)2N]3Sm(μ-Cl)Li(THF)3 in a 2:1 ratio generated the bis(indolyl) heteronuclear bimetallic rare-earth metal amino complex {(η1:η1-[μ-η2:η1-3-(4-Me2N-C6H4CH=N-CH2CH2)C8H5]Li[μ-η2:η1-3-(4-Me2N-C6H4CH=N-CH2CH2)C8H5])Sm[N(SiMe3)2]2} (7) in low yield probably due to accompanying with the formation of the complex 2. The above results indicated that reaction conditions play important roles in the formation of different coordination modes of the imino-functionalized indolyl rare-earth metal amido complexes. All new complexes 1?7 are fully characterized including X-ray structural determination. The catalytic activity of complexes 1-7 for the addition of amines to carbodiimides was explored. The results showed that all complexes displayed an excellent activity towards the addition of amines to carbodiimides producing guanidine under solvent-free condition.
- Yu, Lu,Wang, Fenhua,Wang, Hui,Wang, Shaoyin,Wu, Yunjun,Gu, Xiaoxia
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- Synthesis and Reactivity of NNNNN-Pincer Multidentate Pyrrolyl Rare-Earth-Metal Amido-Chloride or Dialkyl Complexes
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The NNNNN-pincer multidentate pyrrolyl rare-earth-metal amido-chloride complexes {η1:κ3-2,5-[CH3N(CH2CH2)2NCH2]2C4H2N}RECl[N(SiMe3)2] (RE = Y (2a), Sm (2b), Dy (2c), Er (2d), Yb (2e)) were synthesized by one step from reactions of [(Me3Si)2N]3RE(μ-Cl)Li(T
- Cui, Peng,Du, Jun,Huang, Zeming,Sheng, Weiming,Wang, Shaowu,Wei, Yun,Xu, Xiaolong,Zhang, Lijun,Zhang, Xiuli,Zhou, Shuangliu,Zhu, Xiancui
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supporting information
p. 4525 - 4534
(2020/12/22)
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- A silica-supported titanium catalyst for heterogeneous hydroamination and multicomponent coupling reactions
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Highly dehydrated silica gel, SiO2700, gave a material with a total surface hydroxyl density of 0.31 ± 0.05 mmol g-1, 0.9 ± 0.1 Si-OH sites per nm2. Treatment of this material with Ti(NMe2)4/sub
- Aldrich, Kelly E.,Odom, Aaron L.
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p. 11352 - 11360
(2019/08/07)
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- Micelle-Enabled One-Pot Guanidine Synthesis in Water Directly from Isothiocyanate using Hypervalent Iodine(III) Reagents under Mild Conditions
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In this work, we developed a one-pot synthesis of guanidine directly from isothiocyanate using DIB (diacetoxyiodobenzene) as a desulfurizing agent under micellar conditions in water. Our optimization study revealed that the use of 1 % TPGS-750-M as a surfactant with NaOH as an additive base at room temperature can convert a variety of isothiocyanates and amines into corresponding guanidines in excellent yields (69–95 %). This synthetic process in water can be applied to prepare guanidine at gram-scale quantity. Our aqueous micellar medium also demonstrated high reusability as the reaction can be performed for several cycles without losing its efficiency. The reaction is metal-free, utilizes water as solvent and practical (room temperature and open flask).
- Srisa, Jakkrit,Tankam, Theeranon,Sukwattanasinitt, Mongkol,Wacharasindhu, Sumrit
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p. 3335 - 3343
(2019/09/12)
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- 2-Picolylamino(diphenylphosphinoselenoic)amide supported zinc complexes: Efficient catalyst for insertion of N–H bond into carbodiimides, isocyanates, and isothiocyanate
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We report here the hydroamination of heterocumulenes such as carbodiimides, isocyanates, and isothiocyanates by zinc complexes supported by the ligand 2-picolylamino-(diphenylphosphinoselenoic)amide [{(Ph2P-(?Se)}2NCH2(C5H4N)] (1). A series of zinc complexes [κ2-{(Ph2P-(?Se)}2NCH2(C5H4N)ZnX2] [(X?Cl (2), Br (3a), I (4)] were prepared from ligand 1 and the corresponding zinc dihalide in a 1:1 molar ratio at 60°C in a chloroform solvent. The reaction of ligand 1 and ZnBr2 in methanol yielded another zinc complex [κ2-{(Ph2P-(?Se)}2NCH2(C5H4N)ZnBr2(CH3OH)] (3b). The molecular structures of compounds 3a, 3b, and 4 were established through single-crystal X-ray diffraction analyses. The solid-state structures of all the complexes revealed a κ2- chelation through pyridine nitrogen and selenium atoms of ligand 1 to the zinc ion. Complex 2 proved to be a competent pre-catalyst for the addition of the amine N–H bond to carbodiimides, isocyanates, and isothiocyanates. The reaction scope was expanded to reactions of aliphatic and aromatic amines with phenylisocyanate and phenylisothiocyanate in toluene solvents, which proceeded rapidly at room temperature with 5 mol% catalyst loading to yield (up to 99%) the corresponding derivatives of urea and thio-urea. However, a temperature of 90°C was needed for the hydroamination of N,N′ dicyclohexylcarbodiimide. We also report the most plausible mechanism of the hydroamination reaction.
- Harinath, Adimulam,Bano, Kulsum,Ahmed, Shakil,Panda, Tarun K.
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supporting information
p. 23 - 32
(2017/09/25)
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- A new route for the synthesis of functionalized benzothiadiazine 1,1-dioxide derivatives via intramolecular C–H activation reactions of N,N′,N′′-trisubstituted guanidines and benzenesulfonylchloride
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In this study, a simple and appropriate procedure for the synthesis of functionalized benzothiadiazine 1,1-dioxide with good yields via the Cu-catalyzed intramolecular C–H activation reaction from benzenesulfonylchloride and N,N′,N′′-trisubstitutedguanidines, generated by copper(II) oxide-catalyzed hydroamination of carbodiimides, is reported.
- Nazari, Maryam,Nematpour, Manijeh,Rezaee, Elham,Jahani, Mehdi,Tabatabai, Sayyed Abbas
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p. 646 - 655
(2018/08/29)
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- Highly Active Dinuclear Titanium(IV) Complexes for the Catalytic Formation of a Carbon-Heteroatom Bond
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A series of mononuclear titanium(IV) complexes with the general composition κ3-[R{NHPh2P(X)}2Ti(NMe2)2] [R = C6H4, X = Se (3b); R = trans-C6H10, X = S (4a), Se (4b)] and [{κ2-N(PPh2Se)2}2Ti(NMe2)2] (6b) and two dinuclear titanium(IV) complexes, [C6H4{(NPh2PS)(N)}Ti(NMe2)]2 (3c) and [{κ2-N(PPh2Se)}Ti(NMe2)2]2 (6c), are reported. Dinuclear titanium(IV) complex 6c acts as an efficient catalyst for the chemoselective addition of an E-H bond (E = N, O, S, P, C) to heterocumulenes under mild conditions. The catalytic addition of aliphatic and aromatic amines, alcohol, thiol, phosphine oxide, and acetylene to the carbodiimides afforded the corresponding hydroelemented products in high yield at mild conditions with a broader substrate scope. The catalytic efficiency of the dinuclear complex depends on the cooperative effect of the TiIV ions, the systematic variation of the intermetallic distance, and the ligand's steric properties of the complex, which enhances the reaction rate. Most interestingly, this is the first example of catalytic insertion of various E-H bonds into the carbodiimides using a single-site catalyst because only the titanium-mediated insertion of E-H into a C-N unsaturated bond is reported to date. The amine and alcohol insertion reaction with the carbodiimides showed first-order kinetics with respect to the titanium(IV) catalyst as well as substrates. A most plausible mechanism for hydroelementation reaction is also proposed, based on the spectroscopic data of the controlled reaction, a time-course study, and the Hammett plot.
- Bhattacharjee, Jayeeta,Harinath, Adimulam,Banerjee, Indrani,Nayek, Hari Pada,Panda, Tarun K.
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supporting information
p. 12610 - 12623
(2018/10/09)
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- An amidato divalent ytterbium cluster: Synthesis and molecular structure, its reactivity to carbodiimides and application in the guanylation reaction
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A divalent ytterbium amidate 1 ([Yb3L6]·2C7H8 for short) was synthesized via amine-elimination of Yb[N(SiMe3)2]2(TMEDA) with an amide proligand N-2,6-diisopropylphenylbenzamide HL (L = 2,6-iPr2C6H3NC(O)Ph) and structurally characterized to be a trinuclear symmetric cluster. Further studies on the reduction of iPrNCNiPr by complex 1 provide Yb(iii) complex 2 in hexane-THF ([(YbL2)2(μ-NiPrCNiPr)][YbL3(THF)]·C7H8), which is composed of two subunits in a unit cell, one is a bridged Yb(iii) carbene, just the same as complex 4 ([(YbL2)2(μ-NiPrCNiPr)]·3C7H8) obtained in the same reaction in toluene, and the other is a homoleptic monomeric Yb(iii) amidate (YbL3). It is also found that complex 2 decomposed to complex 3 ([YbL3]2·2C7H8) and 4 at 90 °C in toluene. Complexes 1-4 were confirmed by X-ray structure determination. Furthermore, complex 4 was proved to be a more active species than its precursor 1 in the catalytic addition of amines to carbodiimides. Finally, complex 1 was found to be an excellent pre-catalyst for the guanylation reaction with a wide scope of substrates.
- Gong, Chao,Ding, Hao,Lu, Chengrong,Zhao, Bei,Yao, Yingming
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p. 6031 - 6038
(2017/07/10)
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- Copper oxide supported on magnetic nanoparticles (CuO@γ-Fe2O3): An efficient and magnetically separable nanocatalyst for addition of amines to carbodiimides towards synthesis of substituted guanidines
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Copper oxide supported on magnetic nanoparticles was used as a green magnetic nanocatalyst for hydroamination of carbodiimides towards the synthesis of guanidines. Easy preparation and separation, low cost, non-sensitivity to moisture and reusability of the catalyst along with diversity and high yield of products are significant features of this method.
- Abbasi, Sepideh,Saberi, Dariush,Heydari, Akbar
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- A tandem synthesis of 4,5-bis(arylimino)-2-(alkylimino)imidazolidines
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A tandem reaction of aniline derivatives, dialkyl carbodiimides, and bis(imidoyl) chlorides, leads to the formation of functionalized 4,5-bis(arylimino)-2-(alkylimino)imidazolidines, in moderate to good yields. Graphical abstract: [Figure not available: see fulltext.].
- Yavari, Issa,Zahedi, Nooshin,Halvagar, Mohammad Reza
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p. 1439 - 1444
(2017/07/18)
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- Addition of E-H (E = N, P, C, O, S) Bonds to Heterocumulenes Catalyzed by Benzimidazolin-2-iminato Actinide Complexes
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The synthesis and characterization of benzimidazolin-2-iminato actinide(IV) complexes [(BimR1/R2N)An(N{SiMe3}2)3] (An = U, Th) (1-6) is reported. All complexes were obtained in high yields, and their solid state structures were established through single-crystal X-ray diffraction analysis. Using 1-6 as precatalysts, the addition of mono- and bifunctional E-H (E = N, P, C, O, S) substrates to various heterocumulenes, including carbodiimides, isocyanates, and isothiocyanates, was investigated, affording the respective addition products in high yields under very mild reaction conditions. Various amines were applicable to this reaction, indicating a large scope capability of amine nucleophiles for the insertion process.
- Liu, Heng,Fridman, Natalia,Tamm, Matthias,Eisen, Moris S.
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supporting information
p. 3896 - 3903
(2017/10/30)
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- Zinc catalyzed Guanylation reaction of Amines with Carbodiimides/ Isocyanate leading to Guanidines/Urea derivatives formation
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We report the highly chemo-selective catalytic addition of N–H bonds from various aromatic amines to carbodiimides and isocyanates using (Ar-BIAO)ZnCl2 complexes [Ar-BIAO = N-(aryl)imino-acenapthenone, Ar = 2,6-Me2C6H3 (1), 2,4,6 Me3C6H2 (2), 2,6-iPr2C6H3 (3)] as the pre-catalyst to prepare guanidine and urea derivatives in 55-90% yield. The complex 3 showed higher catalytic activity than analogous complexes 1 and 2 under similar reaction conditions. The catalytic guanylation of N–H bonds with heterocumulenes displays a broad substrate scope. The amines having electron donating groups underwent higher conversion than the amines having electron withdrawing groups to afford corresponding guanidine or urea derivatives. A possible mechanism involving penta-coordinated zinc transition state for the catalytic reaction is presented. [Figure not available: see fulltext.]
- Bhattacharjee, Jayeeta,Sachdeva, Mitali,Banerjee, Indrani,Panda, Tarun K
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p. 875 - 881
(2016/07/06)
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- Hydroamination of carbodiimides, isocyanates, and isothiocyanates by a bis(phosphinoselenoic amide) supported titanium(IV) complex
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The hydroamination of heterocumulenes such as carbodiimides, isocyanates, and isothiocyanates by a bis(phosphinoselenoic amide) supported titanium(iv) complex as a precatalyst is reported here. The titanium(iv) complex [{Ph2P(Se)NCH2CH2NPPh2(Se)}Ti(NMe2)2] (1) was synthesised by the reaction of tetrakis-(dimethylamido)titanium(iv) [Ti(NMe2)4] with [{Ph2P(Se)NHCH2CH2NHPPh2(Se)}] in toluene at ambient temperature. Titanium complex 1 proved to be a competent pre-catalyst for the addition of an amine N-H bond to carbodiimides, isocyanates, and isothiocyanates. The reaction scope was expanded to reactions of aliphatic and aromatic amines with phenylisocyanates and phenylisothiocyanates in toluene solvents proceeding rapidly at room temperature with 5 mol% catalyst loadings to yield the corresponding urea and thio-urea derivatives up to 99%. However, ambient temperature was needed for hydroamination of 1,3-dicyclohexylcarbodiimide. The amine addition reactions with isocyanates showed first order kinetics with respect to catalyst 1 as well as substrates. The most plausible mechanism for the hydroamination reaction was established by isolating 1,1-dimethylphenyl urea as a side product.
- Bhattacharjee, Jayeeta,Das, Suman,Kottalanka, Ravi K.,Panda, Tarun K.
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supporting information
p. 17824 - 17832
(2016/11/18)
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- Structural and Mechanistic Insights into s-Block Bimetallic Catalysis: Sodium Magnesiate-Catalyzed Guanylation of Amines
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To advance the catalytic applications of s-block mixed-metal complexes, sodium magnesiate [NaMg(CH2SiMe3)3] (1) is reported as an efficient precatalyst for the guanylation of a variety of anilines and secondary amines with
- De Tullio, Marco,Hernán-Gómez, Alberto,Livingstone, Zoe,Clegg, William,Kennedy, Alan R.,Harrington, Ross W.,Anti?olo, Antonio,Martínez, Antonio,Carrillo-Hermosilla, Fernando,Hevia, Eva
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supporting information
p. 17646 - 17656
(2016/11/29)
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- Isotropic and Oriented Copper Nanoparticles Supported on Graphene as Aniline Guanylation Catalysts
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Adsorption of copper nanoparticles (NPs) on preformed graphene (G) affords an efficient catalyst for the nucleophilic addition of anilines to N,N′-dialkylcarbodiimides to form the corresponding guanidines. Cu/G exhibits a wide scope in promoting guanylati
- Frindy, Sana,El Kadib, Abdelkrim,Lahcini, Mohamed,Primo, Ana,García, Hermenegildo
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p. 3863 - 3869
(2016/07/06)
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- One-Pot Synthesis of C2 Symmetric and Asymmetric N,N′,N″-Substituted Guanidines from Aryl Isothiocyanates and Amines
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Highly substituted guanidines were conveniently prepared through a one-pot reaction between aryl isothiocyanates and amines mediated by the Ph3P-I2/Et3N system. The C 2-symmetric N,N′,N″-substituted guanidines were readily accessed using a 1:2 molar ratio of an aryl isothiocyanate and an amine; while sequential addition of two different amines in equimolar ratios gave rise to asymmetric derivatives. Both primary and secondary amines were found to react preferentially with electron-deficient aryl isothiocyanates, rapidly providing guanidines in good yields under mild conditions.
- Wangngae, Sirilak,Pattarawarapan, Mookda,Phakhodee, Wong
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p. 1121 - 1127
(2016/05/19)
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- Ultrasound-assisted synthesis of substituted guanidines from thioureas
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Ultrasound-assisted synthesis of guanidine derivatives was developed using 2,4,6-trichloro-1,3,5-triazine as an inexpensive dehydrosulfurization reagent. Both 1,3-alkylaryl- and 1,3-diaryl-thioureas were rapidly converted into carbodiimides before subsequent reaction with aromatic or aliphatic amines. The method allows rapid access to highly substituted guanidines in good to excellent yields under mild conditions and with minimal use of solvent.
- Pattarawarapan, Mookda,Jaita, Subin,Wangngae, Sirilak,Phakhodee, Wong
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p. 1354 - 1358
(2018/03/29)
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- Synthesis and characterization of bis(amidate) rare-earth metal amides and their application in catalytic addition of amines to carbodiimides
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Two new bis(amidate) lanthanide amides {LLn[N(SiMe3)2]·THF}2 (H2L = N,N′-(cyclohexane-1,2-diyl)-bis(4-tert-butylbenzamide); Ln = Sm(4), Yb(5)), which were prepared by the treatment of the bridged amide proligand H2L with Ln[N(SiMe3)2]3 in tetrahydrofuran, had been characterized by single-crystal X-ray diffraction and elemental analyses. Both complexes 4 and 5 and the three known isomorphs {LRE[N(SiMe3)2]·THF}2 (RE = La(1), Nd(2), Y(3)) were successfully employed in the addition of amines to carbodiimides for the first time and were found to be efficient catalysts in the transformation at 60°C under solvent-free conditions. The Nd-based catalyst 2 showed the highest reactivity and provided various guanidines with good functional group tolerance in high to excellent yields.
- Cheng, Hao,Xiao, Yang,Lu, Chengrong,Zhao, Bei,Wang, Yaorong,Yao, Yingming
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p. 7667 - 7671
(2015/10/12)
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- Catalytic addition of amines to carbodIImides by bis(β-diketiminate)lanthanide(II) complexes and mechanistic studies
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Reduction reactions of bis(β-diketiminate)lanthanide(iii) chlorides formed in situ by reactions of anhydrous LnCl3 with 2 equiv. of sodium salt of the β-diketiminate ligand in THF with a Na/K alloy afforded a series of bis(β-diketiminate)lanthanide(ii) complexes LnL2(THF)n (L = L26-Me2 = [N(2,6-Me2C6H3)C(Me)]2CH-, n = 1, Ln = Eu (1); L = L2,4,6-Me3 = [N(2,4,6-Me3C6H2)C(Me)]2CH-, n = 1, Ln = Eu (2); L = L2,6-iPr2 = [N(2,6-iPr2C6H3)C(Me)]2CH-, n = 0, Ln = Eu (3), Sm (4); L = L2,6-ipr2Ph = [(2,6-iPr2C6H3)NC(Me)CHC(Me)N(C6H5)]-, n = 0, Ln = Eu (5), Yb (6); L = L2-Me = [N(2-MeC6H4)C(Me)]2CH-, n = 1, Ln = Yb (7)) in high yields. All the complexes, especially the complexes of SmII (4) and EuII (5), were found to be excellent pre-catalysts for catalytic addition of amines to carbodiimides to multi-substituted guanidines with a wide scope of substrates. The activity depends both on the central metals and the ligands with the active sequence of YbII II and EuII II and L2,6-Me2 2,4,6-Me3 ~ L2,6-iPr2 2,6-ipr2Ph for the ligands. The mechanistic study by the isolation of guanidinate species and their reactivity revealed that EuII monoguanidinate complexes Eu(L2,6-Me2)[(C6H5N)C(NHCy)(NCy)](DME) (8) and Eu(L2,6-ipr2Ph)[(C6H5N)C(NHCy)(NCy)](THF)2 (9) should be the key active intermediates for the systems with EuII complexes and a YbIII bis(guanidinate) complex Yb(L2-Me)[(C6H5N)C(NHCy)(NCy)]2 (11) for the system using a YbII complex.
- Xue, Mingqiang,Zheng, Yu,Hong, Yubiao,Yao, Yingming,Xu, Fan,Zhang, Yong,Shen, Qi
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supporting information
p. 20075 - 20086
(2015/12/01)
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- Aluminum alkyl complexes supported by bidentate N,N ligands: Synthesis, structure, and catalytic activity for guanylation of amines
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The reactions of AlMe3 or AlEt3 with 2-pyridyl- or indolyl-substituted imines were studied, leading to the formation of different organoaluminum complexes. While the reactions of the iminopyridine Cy[N=CMe-2-(C5H4N)]2 (L1) derived from 1-(pyridin-2-yl)ethanone and trans-1,2-cyclohexanediamine with AlEt3 gave the aluminum complex Cy[NC(Me)(Et)-2-(C5H4N)AlEt2]2 (1), in which the two ketimine groups of the ligand were transformed into the amido functionality through the addition of two ethyl groups, the reaction of L1 with AlMe3 afforded the aluminum complex Cy[NC(=CH2)-2-(C5H4N)AlMe2]2 (2) via a sp3 C-H activation with elimination of two methane molecules. The reactions of indolyl-2-aldimines (2-(RN=CH)C8H5NH (R = tBu (L2H), C6H5 (L3H), 2,6-Me2C6H3 (L4H)) with AlMe3 or AlEt3 afforded only the deprotonated indolyl aluminum complexes [2-(RN=CH)C8H5N]AlMe2 (R = tBu (3), C6H5 (4), 2,6-Me2C6H3 (5)) and [2-(2,6-Me2C6H3N=CH)C8H5N]AlEt2 (6), respectively. The structures of complexes 2-6 were characterized by spectral methods and X-ray crystallographic analyses. These aluminum complexes showed a high catalytic activity in the addition of amines to carbodiimides to form guanidines. The mechanism of the catalytic process was studied by control experiments and 1H NMR monitoring. Together with the isolation of the complex [2-(2,6-Me2C6H3N=CH)C8H5N][CyN=C(4-MeC6H3N)(NHCy)]AlMe (7), a probable mechanism for the guanylation reaction was proposed.
- Wei, Yun,Wang, Shaowu,Zhou, Shuangliu,Feng, Zhijun,Guo, Liping,Zhu, Xiancui,Mu, Xiaolong,Yao, Fangshi
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p. 1882 - 1889
(2015/06/08)
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- Phenylene-bridged β-Ketoiminate Dilanthanide Aryloxides: Synthesis, Structure, and Catalytic Activity for Addition of Amines to Carbodiimides
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The synthesis and reactivity of a series of bimetallic lanthanide aryloxides stabilized by a p-phenylene-bridged bis(β-ketoiminate) ligand is presented. The reaction of 1,4-diaminobenzene with acetylacetone in a 1:2.5 molar ratio in absolute ethanol gave
- Hong, Yubiao,Zheng, Yu,Xue, Mingqiang,Yao, Yingming,Zhang, Yong,Shen, Qi
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supporting information
p. 1230 - 1237
(2015/06/30)
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- Catalytic C-N bond formation in guanylation reaction by N-heterocyclic carbene supported magnesium(II) and zinc(II) amide complexes
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The catalytic activity of N-heterocyclic carbene (NHC) supported magnesium(II) and a zinc(II) amide complex towards the addition of N-H bond of amine to carbodiimide was studied. Treatment of a free carbene i.e., 1,3-di-tert-butylimidazol-2-ylidene (ItBu) with magnesium and zinc bis(amide) i.e., M[N(SiMe3)2]2, M = Mg or Zn in toluene led to the formation of ItBu:M[N(SiMe3) 2]2, M = Mg(1) and Zn(2) compounds, respectively. Both 1 and 2 were characterized by multinuclear (1H, 13C and 29Si) NMR spectroscopy and single X-ray crystal structure analysis. Solid state structures revealed that both complexes are monomeric in nature and their magnesium and zinc atoms are three coordinated and distorted trigonal planar in geometries. Furthermore, compounds 1 and 2 were tested as catalysts for the guanylation reaction of addition of amine to carbodiimide and turned to be excellent catalysts.
- Baishya, Ashim,Barman, Milan Kr.,Peddarao, Thota,Nembenna, Sharanappa
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p. 112 - 118
(2014/09/17)
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- Cyclopentadienyl-like ligand as a reactive site in half-sandwich bis(amidinato) rare-earth-metal complexes: An efficient application in catalytic addition of amines to carbodiimides
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A series of mixed Cp′/bis(amidinato) (Cp′ = η5-C5Me4(SiMe3)) lanthanide complexes were synthesized by the 1:2 acid-base reaction between Cp′Ln(CH2SiMe3)2(THF) (Ln = Y, Dy, Er, Lu
- Wei, Peng-Hui,Xu, Ling,Song, Li-Cheng,Zhang, Wen-Xiong,Xi, Zhenfeng
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p. 2784 - 2789
(2014/06/24)
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- Mechanistic insights into N - N bond cleavage in catalytic guanylation reactions between 1,2-diarylhydrazines and carbodiimides
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Cleavage of the N - N bond in 1,2-diarylhydrazine was achieved through an alkyllithium-catalyzed guanylation reaction of 1,2-diarylhydrazine with carbodiimide, affording guanidine and azo compounds. This N - N bond cleavage via thermal rearrangement was d
- Xu, Ling,Wang, Yu-Chen,Ma, Wangyang,Zhang, Wen-Xiong,Xi, Zhenfeng
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p. 12004 - 12009
(2015/02/19)
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- Bridged bis(amidinate) lanthanide aryloxides: Syntheses, structures, and catalytic activity for addition of amines to carbodiimides
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Various lanthanide aryloxide complexes supported by bridged bis(amidinate) ligand L, LLnOAr(DME) (L = Me3SiNC(Ph)N(CH2) 3NC(Ph)NSiMe3, DME = dimethoxyethane, Ln = Y, Ar = 2,6-(Me)2C6H3
- Tu, Jing,Li, Wenbo,Xue, Mingqiang,Zhang, Yong,Shen, Qi
-
supporting information
p. 5890 - 5901
(2013/07/19)
-
- Synthesis of guanidines from amines and carbodiimides catalyzed by mono-indenyl-ligated rare earth metal bis(silylamide) complexes
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Nucleophilic addition of primary aromatic amines to carbodiimides in the presence of catalytic amount of the mono-indenyl-ligated rare earth metal bis(silylamide) complexes (C9H6CMe2CH 2C5H4N-α)Ln[N(SiHMe2) 2]2 at room temperature afforded efficiently a series of guanidines with a wide spectrum of substituents on the nitrogen atoms. Nucleophilic addition of primary aromatic amines to carbodiimides promoted by the mono-indenyl-ligated rare earth metal bis(silylamide) complexes (C 9H6CMe2CH2C5H 4N-α)Ln[N(SiHMe2)2]2 afforded a series of guanidines. Copyright
- Chen, Jue,Wang, Yibin,Luo, Yunjie
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p. 1065 - 1071
(2013/09/02)
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- β-Diketiminatoytterbium aryloxides: Synthesis, structural characterization, and catalytic activity for addition of amines to carbodiimides
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The steric effect of an aryloxido group on the synthesis and molecular structures of ytterbium aryloxides supported by β-diketiminato ligand L (L = [N(2,6-Me2C6H3)C(Me)]2CH -) is reported. Reactions o
- Cai, Ling-Xia,Yao, Ying-Ming,Xue, Ming-Qiang,Zhang, Yong,Shen, Qi
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p. 366 - 372
(2013/07/28)
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- Synthesis of substituted guanidines using Zn-Al hydrotalcite catalyst
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Substituted guanidines were synthesized by the guanylation of amines with carbodiimides using Zn-Al hydrotalcite (Zn-Al HT) catalyst. Zn-Al HT was prepared by co-precipitation method and characterized by X-ray powder diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Raman and Thermogravimetric-Differential Thermal Analysis (TG-DTA). The heterogeneous catalyst afforded moderate to good yields (~50-60 %) of substituted guanidines in toluene at 110?C in 12 h. The catalyst was recovered quantitatively by simple filtration and reused for three cycles with consistent activity. The XRD and FTIR studies of the used catalyst shows no variation in the structure of the catalyst even after three recycles. Indian Academy of Sciences.
- Mannepalli, Lakshmi Kantam,Dupati, Venkanna,Vallabha, Swarna Jaya,Sunkara, V Manorama
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p. 1339 - 1345
(2014/04/03)
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- Construction of oxygen-bridged multimetallic assembly: Dual catalysts for hydroamination reactions
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Herein, we utilized multiple metal centers of a single catalytic system for two different activation processes in hydroamination catalysis. A trimetallic complex, [Cp*2(Me)Zr(μ-O)Zr(NMe2) 2(μ-O)Zr(Me)Cp*2] (2) b
- Mukherjee, Arup,Sen, Tamal K.,Mandal, Swadhin K.,Maity, Bholanath,Koley, Debasis
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p. 1255 - 1264
(2013/03/14)
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- Catalytic guanylation of aliphatic, aromatic, heterocyclic primary and secondary amines using nanocrystalline zinc(II) oxide
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Nanocrystalline ZnO was found to be a highly efficient heterogeneous catalyst for the guanylation of amines with various carbodiimides to afford N,N′,N″-trisubstituted guanidines in excellent yields. Structurally divergent aliphatic, aromatic, heterocyclic primary and secondary amines were converted to the corresponding N,N′,N″-trisubstituted guanidines using optimal conditions. The catalyst was easy to handle even under atmospheric conditions and can be easily recovered by centrifugation and reused for five cycles with consistent activity.
- Kantam, M. Lakshmi,Priyadarshini,Amal Joseph,Srinivas,Vinu,Klabunde,Nishina, Yuta
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experimental part
p. 5730 - 5737
(2012/09/08)
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- Metal-free synthesis of cyclic di-oxoguanidines via one-pot sequential transformation of amines, carbodiimides and acyl dichlorides
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The one-pot sequential reaction of various amines, carbodiimides, and acyl dichlorides has been achieved for the first time under metal-free conditions to provide symmetric cyclic di-oxoguanidines via an unexpected 2,2-dichloro- imidazolidindione intermed
- Zhao, Fei,Wang, Yang,Zhang, Wen-Xiong,Xi, Zhenfeng
-
supporting information; experimental part
p. 6266 - 6270
(2012/09/05)
-
- Rare-earth metal tris(trimethylsilylmethyl) anionic complexes bearing one 1-phenyl-2,3,4,5-tetrapropylcyclopentadienyl ligand: Synthesis, structural characterization, and application
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Synthesis and structural characterization of half-sandwich rare-earth metal tris(trimethylsilylmethyl) anionic complexes bearing one 1-phenyl-2,3,4,5- tetrapropylcyclopentadienyl ligand are achieved. These soluble anionic compounds show good reactivity in
- Xu, Ling,Wang, Zitao,Zhang, Wen-Xiong,Xi, Zhenfeng
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p. 11941 - 11948,8
(2020/10/15)
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- First iron-catalyzed guanylation of amines: A simple and highly efficient protocol to guanidines
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The first iron-catalyzed guanylation of amines is reported. Commercially available Fe(OAc)2 acts as an excellent catalyst for the addition of amines to carbodiimides. The reaction is broadly applicable to a variety of primary, secondary, and heterocyclic amines, and tolerates a wide range of functionalities allowing the easy preparation of a large family of guanidines. The low price and low toxicity of the commercially available iron catalyst make this methodology highly attractive.
- Pottabathula, Srinivas,Royo, Beatriz
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supporting information; experimental part
p. 5156 - 5158
(2012/09/22)
-
- O-Iodoxybenzoic acid mediated oxidative condensation: Synthesis of guanidines using 1,-3-disubstituted thiourea precursors
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An efficient and mild oxidative condensation procedure using o-iodoxybenzoic acid and triethylamine or ammonia as base has been developed for the synthesis of guanidines starting from easily synthesizable 1,3-disubstituted thioureas and amines or ammonia.
- Dangate, Prasad S.,Akamanchi, Krishnacharya G.
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p. 6765 - 6767
(2013/01/15)
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- Heterobimetallic dianionic guanidinate complexes of lanthanide and lithium: Highly efficient precatalysts for catalytic addition of amines to carbodiimides to synthesize guanidines
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A series of heterobimetallic dianionic guanidinate complexes of lanthanide and lithium, [Li(THF)(DME)]3Ln[μ- η2η1(iPrN)2C(NC 6H4p-R)]3 [R=Cl, Ln=Nd (I), Y (II), La (III); R=H, Ln=Nd (IV)] were synthesized and fully characterized. These complexes were found to be highly efficient precatalysts for the addition of various primary and secondary amines, and aromatic and aliphatic diamines to carbodiimides to give the corresponding monoguanidine and biguanidine derivatives under mild condition (at 25-60 °C), which provides an efficient way for the synthesis of biguanidines compounds. The activity depends on the central metals and ligands: La>Nd>Y for the metals and [(iPrN) 2C(NC6H4p-Cl)]2->[( iPrN)2C(NC6H5)]2- for the ligands were observed.
- Zhang, Xingmin,Wang, Chuanyong,Qian, Cunwei,Han, Fubin,Xu, Fan,Shen, Qi
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experimental part
p. 8790 - 8799
(2011/12/02)
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- Activation of carbodiimide and transformation with amine to guanidinate group by Ln(OAr)3(THF)2 (Ln: Lanthanide and yttrium) and Ln(OAr)3(THF)2 as a novel precatalyst for addition of amines to carbodiimides: Inf
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Reaction of Ln(OAr1)3(THF)2 (Ar 1= [2,6-(tBu)2- 4-MeC6H2] with carbodiimides (RNCNR) in toluene afforded the RNCNR coordinated complexes (Ar 1O)3Ln(NCNR) (R = iPr (iso
- Cao, Yang,Du, Zhu,Li, Wenbo,Li, Junmei,Zhang, Yong,Xu, Fan,Shen, Qi
-
experimental part
p. 3729 - 3737
(2011/07/07)
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- Influence of Schiff base and lanthanide metals on the synthesis, stability, and reactivity of monoamido lanthanide complexes bearing two Schiff bases
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The monoamido lanthanide complexes stabilized by Schiff base ligand L 2LnN(TMS)2 (L = 3,5-But2-2-(O)- C6H2CH=N-8-C9H6N, Ln = Yb (1), Y (2), Eu (3), Nd (4), and La (5))
- Han, Fubin,Teng, Qiaoqiao,Zhang, Yong,Wang, Yaorong,Shen, Qi
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experimental part
p. 2634 - 2643
(2011/06/18)
-
- Highly efficient aluminum-catalyzed hydro-amination/-hydrazination of carbodiimides
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The catalytic activity of commercially available [Al(NMe2) 3]2 (1) and a dimethyl aluminum guanidinate complex toward the hydro-amination/-hydrazination of carbodiimides was studied. The guanidinate-supported complex 2 was
- Koller, Juergen,Bergman, Robert G.
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experimental part
p. 5946 - 5952
(2011/02/23)
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- Zn(OTf)2-catalyzed addition of amines to carbodiimides: Efficient synthesis of guanidines and unpredicted formation of Zn-N amido species
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Zn(OTf)2 acts as an excellent catalyst precursor for addition of various amine N-H bonds to carbodiimides under an atmosphere of air, offering a convenient synthesis of substituted guanidines with high functional-group tolerance. A Zn-N amido species is shown to act as the active species.
- Li, Dongzhen,Guang, Jie,Zhang, Wen-Xiong,Wang, Yang,Xi, Zhenfeng
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experimental part
p. 1816 - 1820
(2010/08/21)
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- Rare earth metal bis(trimethylsilyl)amido complexes bearing pyrrolyl-methylamide ligand. Synthesis, structure, and catalytic activity towards guanylation of amines
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The N-arylaminomethyl substituted pyrrolyl ligand 2-[(2,4,6-Me 3C6H2)NHCH2](C4H 3NH) (1) was synthesized by reduction of 2-[(2,4,6-Me 3C6H2)NCH](C4H3NH) using NaBH4. Treatment of [(Me3Si)2N] 3Ln(μ-Cl)Li(THF)3 with 1 equiv. of 1 in reflux toluene for 24 h, afforded the corresponding trivalent rare earth metal amides with formula {(μ-η5:η1):η1-2-[(2,4,6- Me3C6H2)NCH2]C4H 3N]LnN(SiMe3)2}2 (Ln = Y(2), Nd(3), Sm(4), Dy(5), Er(6)). All compounds were fully characterised by spectroscopic methods and elemental analyses. The structures of complexes 2, 4 and 6 were determined by single-crystal X-ray analyses. X-Ray analyses discovered that two rare-earth metal ions were bridged by dianion ligand with the pyrrolyl ring which coordinated to one rare earth metal in an η5 mode, the tethered nitrogen anion and nitrogen atom of the pyrrolyl ring coordinated to another rare earth metal in η1 modes forming the centrosymmetric dinuclear structures. The rare earth metal complexes as catalysts for the guanylation of aromatic amines were studied. Results showed all rare earth metal complexes exhibited a high catalytic activity on the guanylation of aromatic amines. The Royal Society of Chemistry 2010.
- Liu, Chao,Zhou, Shuangliu,Wang, Shaowu,Zhang, Lijun,Yang, Gaosheng
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experimental part
p. 8994 - 8999
(2011/01/08)
-
- CURABLE COMPOSITION
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The present invention has its object to provide a curable composition which comprises a guanidine compound as a non-organotin type catalyst, is less discolored, has good surface curability, depth curability, strength rise and adhesiveness, and can retain the curability even after storage; the above object can be achieved by a curable composition which comprises: (A) an organic polymer containing a silyl group capable of crosslinking under siloxane bond formation, the silyl group being a group represented by the general formula (1): -SiX 3 (1) (wherein X represents a hydroxyl group or a hydrolyzable group and the three X groups may be mutually the same or different), (B) a guanidine compound (B-1) as a silanol condensation catalyst, and (C) a plasticizer, wherein the content of the component (B-1) is not lower than 0.1 part by weight but lower than 8 parts by weight per 100 parts by weight of the component (A), and a non-phthalate ester plasticizer accounts for 80 to 100% by weight of the (C) component plasticizer.
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-
- Ytterbium triflate: A highly active catalyst for addition of amines to carbodiimides to N,N′,N″-trisubstituted guanidines
-
(Chemical Equation Presented) Ytterbium triflate was found to be efficient catalyst for addition of amines to carbodiimides to N,N′,N″- trisubstituted guanidines with a wide scope of amines under solvent-free condition.
- Zhu, Xuehua,Du, Zhu,Xu, Fan,Shen, Qi
-
supporting information; experimental part
p. 6347 - 6349
(2009/12/08)
-
- Titanacarborane mediated C-N bond forming/breaking reactions
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Constrained-geometry titanacarboranes [σ:η1:η5-(OCH2)(R2NCH2)C2B9H9]Ti(NR2) (R = Me, Et) are synthesized via an unexpected reaction of [Me3NH][μ-7,8-CH2OCH2-7,8-C2B9H10] with Ti(NR2)4 (R = Me, Et), involving a C-O bond cleavage and C-N bond formation. These complexes can be readily converted to new amide species or alkoxide by reacting with amines or esters, respectively. Insertion of a series of unsaturated molecules into the Ti-N bond of the aforementioned complexes results in the formation of various half-sandwich titanacarboranes. [σ:η1:η5-(OCH2)(Me2NCH2)C2B9H9]Ti(NMe2) is also able to efficiently catalyze the hydroamination of carbodiimides and the transamination of guanidines. These results are summarized in this brief account.
- Shen, Hao,Xie, Zuowei
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scheme or table
p. 1652 - 1657
(2009/10/11)
-
- Divalent lanthanide complexes: Highly active precatalysts for the addition of N-H and C-H bonds to carbodiimides
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(Chemical Equation Presented) Various divalent lanthanide complexes with the formula LnL2(sol)x (L = N(TMS)2, sol = THF, x = 3, Ln = Sm (I), Eu (II), Yb (III); L = MeC5H4, sol = THF, x = 2, Ln = Sm (IV); L = ArO(Ar = [2,6-(tBu)2-4- MeC6H2]), sol = THF, x = 2, Ln = Sm (V)), especially complexes I-III, serve as excellent catalyst precursors for catalytic addition of various primary and secondary amines to carbodiimides, efficiently providing the corresponding guanidine derivatives with a wide range of substrates under solvent-free condition. The reaction shows good functional groups tolerence. Complexes I-III are also excellent precatalysts for addition of terminal alkynes to carbodiimides yielding a series of propiolamidines. The active sequence of Yb 5H4 2 for ligand around the metal was observed for both reactions. The first step in both reactions was supposed to include the formation of a bimetallic bisamidinate samarium species originating from the reduction-coupling reaction of carbodiimide promoted by lanthanide(II) complex. The active species is proposed to be a lanthanide guanidinate and a lanthanide amidinate.
- Du, Zhu,Li, Wenbo,Zhu, Xuehua,Xu, Fan,Shen, Qi
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supporting information; experimental part
p. 8966 - 8972
(2009/04/06)
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- Heavier group-2-element catalyzed hydroamination of carbodiimides
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The heteroleptic calcium amide [{ArNC(Me)CHC(Me)-NAr}Ca{N(SiMe 3)2}(THF)] (Ar = 2,6-diisopropylphenyl) and the homoleptic heavier alkaline earth amides, [M{N(Si-Me3)2} 2(THF)2] (M = Ca, Sr and Ba) are
- Lachs, Jennifer R.,Barrett, Anthony G. M.,Crimmin, Mark R.,Kociok-Koehn, Gabriele,Hill, Michael S.,Mahon, Mary F.,Procopiou, Panayiotis A.
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experimental part
p. 4173 - 4179
(2009/02/07)
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