Structure of 29841-69-8
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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
4.5
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Jankowska, Dominika ; Lakomska, Iwona ; Muziol, Tadeusz M ; Skowronski, Lukasz ; Rerek, Tomasz ; Popielarski, Pawel , et al.
Abstract: 3+3 optically active macrocyclic Schiff bases were synthesized in the reaction between 4-tert-butyl-2,6-diformylphenol with (1R,2R)-(+)-1,2-diphenylethylenediamine or (1S,2S)-(−)-1,2-diphenylethylenediamine (S1a). The new compounds were spectroscopically characterised by NMR, IR, X-ray (S1a), UV–Vis and fluorescence spectroscopy. The S1a molecule creates channels with distances between oxygen atoms ranging from 5.8-6.3 Å and sufficiently large to host acetonitrile molecule. Both compounds exhibit green-yellow emission in solution and solid state. Thin layers of the S1 compound obtained via Molecular Beam Epitaxy (MBE) were characterised by scanning electron microscopy with energy-dispersive X-ray spectroscopy SEM/EDS and atomic force microscopy (AFM). The optical properties of the S1/Si thin material were analysed using spectroscopic ellipsometry (SE), fluorescence spectroscopy and synchrotron radiation (SR). The time constant for the decay investigated under SR, denoted by τ1, was determined to be approximately 1.02 ns, suggesting a fast deactivation process of the excited electronic state in the S1/Si material. The ellipsometric analysis of the S1/Si layer showed semiconducting behaviour with pronounced absorption features in the UV range, attributed to π → π* and n → π* transitions, characteristic of Schiff bases. The band-gap energy, determined using the Tauc method, is 3.46 ± 0.01 eV. These analyses highlight the material’s potential in applications requiring precise control of optical properties. In the emission spectrum of S1a, a significant emission peak of approximately 561 nm indicates the presence of a prominent emissive process within this wavelength. The S1a compound is emissive in the yellow-green region of the spectrum and has a longer decay time, which suggests that it can be used in sensing optical technologies.
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Reactivity variance between stereoisomers of saturated N-heterocyclic carbenes on gold surfaces
Kaur, Gurkiran ; Dominique, Nathaniel L. ; Hu, Gaohe ; Nalaoh, Phattananawee ; Thimes, Rebekah L. ; Strausser, Shelby L. , et al.
Abstract: Controlling the chirality of mol.-surface systems is essential for applications ranging from heterogeneous catalysis to biosensing. N-heterocyclic carbenes (NHCs) are quickly becoming a dominant ligand for noble metal surface passivation, but the potential of chiral NHC scaffolds remains untapped. In this work, two stereoisomers, one C2 sym. and one Cs sym., of saturated N-heterocyclic carbenes (NHCs) and a structurally related unsaturated NHC (C2v sym.) were synthesized as NHC-CO2 adducts. These CO2-protected NHCs were deposited on gold films and their presence on the films was confirmed by laser desorption ionization mass spectrometry (LDI-MS) and surface enhanced Raman spectroscopy (SERS). Surprisingly, the Cs NHC, but not the chiral C2 NHC, partially degrades to the independently synthesized unsaturated NHC upon binding to the gold. Theor. calculations assist in explaining this phenomenon by showing that the NHCs primarily lie flat on the gold surfaces, which exposes the backbone protons on the Cs-sym. NHC to a formal elimination of H2, while the C2-sym. NHC remains protected from this elimination reaction. These results raise critical questions as to how the structure of NHC ligands may be tuned to influence binding and reactivity on gold surfaces.
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Jameson ; Bailey Lauren ;
Abstract: Enantioselective additions of malonate esters to nitroalkenes can be catalyzed by a variety of salts of chiral cobalt(III) trications [Co(1,2-diamine)3] 3+ in the presence of nitrogen donor bases in acetone. Catalysts that feature enantiopure 1,2-diphenylethylenediamine are particularly effective, and the base can also be incorporated into one of the counter anions, for example a (substituted) nicotinate. This study shows that such additions can be carried out under solvent free conditions and with reduced reaction times using ball milling, further enhancing the "green" credentials of this large family of earth-abundant-metal catalysts. The effect of various reaction variables are probed (base, counter anions, loading, time, quantity of balls, etc.), and the optimized conditions applied to twelve nitroalkenes, affording products in average yields and ee values of 89% and 74%. The enantioselectivities appear slightly lower than for analogous reactions in solution (0 °C), and possible factors and remedies are discussed. These tricationic Co(III) species were also analyzed using Electrospray Ionization-Mass Spectrometry to determine if the anions “fly” with the cation for further mechanistic analysis. Only half showed anions “flying” with the cation: Λ-(S,S)-23+ 2Cl–, Λ/D-(S,S)-23+ 2Cl–BArf –, Λ-(S,S)-23+ Cl–BArf –Nic–, and Λ-(S,S)-23+ 3BF4 –. While anionic impurities were found in several cases, the larger, bulkier anions seemed to become ionized themselves leaving no indication of intact cation-anion species post-ionization. Enhanced purification techniques are shown to improve the removal of unwanted anions.
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Connor Q. Kabes ; William J. Maximuck ; Subrata K. Ghosh ; Anil Kumar ; Nattamai Bhuvanesh ; John A. Gladysz
Abstract: The enantiopure and diastereopure salts Λ- or Δ-[Co((S,S)-dpen)3]3+ 2Cl–BArf– (Λ- or Δ-(S,S)-13+ 2Cl–BArf–; dpen/BArf = 1,2-diphenylethylenediamine/B(3,5-C6H3(CF3)2)4) and Λ-(S,S)-13+ 3Cl– are treated with salts of the enantiopure chiral monoanions (A–) or dianions (A2–) 3-bromocamphor-8-sulfonate (camphSO3–), 1,1′-binaphthyl-2,2′-diyl phosphate (and three 3,3′-disubstituted derivatives), a related biphenanthryl species, tartrate, and Sb2(tart′)22– (tart′ = [−O2C–CHO––CHO––CO2–]). The lipophilic salts Λ- or Δ-(S,S)-13+ 2A–BArf–, Λ-(S,S)-13+ A2–BArf–, and Λ-(S,S)-13+ 3A– are isolated as hydrates and characterized by NMR and microanalyses. In the presence of tertiary amines, many of these are highly enantioselective catalysts for additions of 1,3-dicarbonyl compounds to trans-β-nitrostyrene and di-tert-butylazodicarboxylate. The ee values for diastereomeric salts can exhibit significant differences (avg/high/median Δ%ee = 10/63/6; matched/mismatched effect), and in a few cases, they are better than those obtained with Λ- or Δ-(S,S)-13+ 2Cl–BArf–. The crystal structure of Δ-(S,S)-13+ 2(1S)-camphSO3–BArf– shows that the two sulfonate moieties hydrogen-bond to opposite (idealized) C3-symmetric faces of the trication, with a separate oxygen atom associated with each of the three synperiplanar NH groups.
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Keywords: cobalt ; 1,2-diamines ; chiral anions ; hydrogen bonding ; enantioselective catalysis ; Michael additions ; matched/mismatched
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CAS No. : | 29841-69-8 |
Formula : | C14H16N2 |
M.W : | 212.29 |
SMILES Code : | N[C@@H](C1=CC=CC=C1)[C@H](C2=CC=CC=C2)N |
MDL No. : | MFCD00082751 |
InChI Key : | PONXTPCRRASWKW-KBPBESRZSA-N |
Pubchem ID : | 6931238 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
Num. heavy atoms | 16 |
Num. arom. heavy atoms | 12 |
Fraction Csp3 | 0.14 |
Num. rotatable bonds | 3 |
Num. H-bond acceptors | 2.0 |
Num. H-bond donors | 2.0 |
Molar Refractivity | 66.12 |
TPSA ? Topological Polar Surface Area: Calculated from |
52.04 Ų |
Log Po/w (iLOGP)? iLOGP: in-house physics-based method implemented from |
2.11 |
Log Po/w (XLOGP3)? XLOGP3: Atomistic and knowledge-based method calculated by |
1.4 |
Log Po/w (WLOGP)? WLOGP: Atomistic method implemented from |
1.74 |
Log Po/w (MLOGP)? MLOGP: Topological method implemented from |
2.41 |
Log Po/w (SILICOS-IT)? SILICOS-IT: Hybrid fragmental/topological method calculated by |
2.17 |
Consensus Log Po/w? Consensus Log Po/w: Average of all five predictions |
1.97 |
Log S (ESOL):? ESOL: Topological method implemented from |
-2.4 |
Solubility | 0.855 mg/ml ; 0.00403 mol/l |
Class? Solubility class: Log S scale |
Soluble |
Log S (Ali)? Ali: Topological method implemented from |
-2.1 |
Solubility | 1.7 mg/ml ; 0.008 mol/l |
Class? Solubility class: Log S scale |
Soluble |
Log S (SILICOS-IT)? SILICOS-IT: Fragmental method calculated by |
-4.3 |
Solubility | 0.0106 mg/ml ; 0.0000501 mol/l |
Class? Solubility class: Log S scale |
Moderately soluble |
GI absorption? Gatrointestinal absorption: according to the white of the BOILED-Egg |
High |
BBB permeant? BBB permeation: according to the yolk of the BOILED-Egg |
Yes |
P-gp substrate? P-glycoprotein substrate: SVM model built on 1033 molecules (training set) |
Yes |
CYP1A2 inhibitor? Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set) |
No |
CYP2C19 inhibitor? Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set) |
No |
CYP2C9 inhibitor? Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set) |
No |
CYP2D6 inhibitor? Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set) |
No |
CYP3A4 inhibitor? Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set) |
No |
Log Kp (skin permeation)? Skin permeation: QSPR model implemented from |
-6.6 cm/s |
Lipinski? Lipinski (Pfizer) filter: implemented from |
0.0 |
Ghose? Ghose filter: implemented from |
None |
Veber? Veber (GSK) filter: implemented from |
0.0 |
Egan? Egan (Pharmacia) filter: implemented from |
0.0 |
Muegge? Muegge (Bayer) filter: implemented from |
0.0 |
Bioavailability Score? Abbott Bioavailability Score: Probability of F > 10% in rat |
0.55 |
PAINS? Pan Assay Interference Structures: implemented from |
0.0 alert |
Brenk? Structural Alert: implemented from |
0.0 alert: heavy_metal |
Leadlikeness? Leadlikeness: implemented from |
No; 1 violation:MW<1.0 |
Synthetic accessibility? Synthetic accessibility score: from 1 (very easy) to 10 (very difficult) |
1.98 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine; In dichloromethane; at 0 - 20℃; for 5h; | General procedure: To a stirred solution of triethylamine (1.39 mL, 10 mmol) and (1S,2S)-1,2-diphenylethane-1,2-diamine (1.06 g, 5 mmol) in CH2Cl2 (15 mL) at 0 C, (1S)-(+)-10-camphorsulfonyl chloride 1 (1.25 g, 5 mmol) in CH2Cl2 (5 mL) was added dropwise. Then after stirring at the same temperature for 1 h, and then at room temperature for another 4 h, the reaction mixture was quenched with water and extracted with CH2Cl2. The organic phase was separated and dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by crystallization with ethyl acetate and methanol to afford (S,S,S)-CsDPEN as a white solid (1.04 g, 48% yield). |
Tags: 29841-69-8 synthesis path| 29841-69-8 SDS| 29841-69-8 COA| 29841-69-8 purity| 29841-69-8 application| 29841-69-8 NMR| 29841-69-8 COA| 29841-69-8 structure
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