56671-81-9Relevant articles and documents
Fluorophobic Effect Promoting Lamellar Self-Assembly of Donor Acceptor Dyes
Haenle, Johannes Christian,St?ckl, Yannick,Forschner, Robert,Haenle, Elena,Laschat, Sabine
, p. 2758 - 2767 (2018)
To combine liquid crystalline and linear optical properties in the same molecule, the fluorophobic effect was probed for the first time in donor acceptor dyes. Thus, a series of mono-, bi-, and tricyclic donor acceptor dyes with 1H,1H-perfluorinated alkyl chains of different lengths as donor units and nitrile, malononitrile or barbiturate as acceptor units was synthesized in 5 steps and 1.4–6.6 % overall yield. UV/Vis and fluorescence spectroscopy, cyclic voltammetry and DFT calculations revealed that absorption and emission maxima, Stokes shifts and LUMO energies were mainly governed by the chromophore size and acceptor strengths. The perfluorinated chain was electronically almost decoupled from the remaining chromophore and induced only slight changes of the absorption maxima as compared to the alkyl substituted counterparts. However, in contrast to the non-mesomorphic alkyl donor-substituted derivatives, the perfluorinated donors resulted in self-assembly into partially interdigitated SmA bilayers according to differential scanning calorimetry (DSC), polarizing optical microscopy (POM), X-ray diffraction (WAXS, SAXS) studies and electron density profile calculations.
Stereoselective Synthesis of the Core Structures of Pyrrocidines and Wortmannines through the Excited-State Nazarov Reactions
Xue, Dongsheng,Que, Yonglei,Shao, Hao,He, Haibing,Zhao, Xiaoli,Gao, Shuanhu
supporting information, p. 2736 - 2741 (2021/05/05)
The reaction conditions and scope of the excited-state Nazarov reaction of dicyclicvinyl ketones were studied. The stereochemistry of this electrocyclization is consistent with the mechanism of the pericyclic reaction and Woodward-Hoffmann rule. UV-light-promoted excited-state Nazarov reactions gave hydrofluorenones bearing a syn-cis configuration via a disrotatory cyclization. The core tricyclic hydrofluorenones of pyrrocidines and wortmannines were constructed via the excited-state Nazarov reactions, which demonstrated their synthetic potential in complex natural product total synthesis.
A ring-locking strategy to enhance the chemical and photochemical stability of A-D-A-type non-fullerene acceptors
Liu, Hongtao,Wang, Wen,Zhou, Yinhua,Li, Zhong'An
supporting information, p. 1080 - 1088 (2021/01/25)
Recently, the power conversion efficiencies (PCEs) of bulk-heterojunction organic solar cells (BHJ-OSCs) based on non-fullerene acceptors (NFAs) have made a very impressive progress in the research field. However, less attention has been paid to the intrinsic chemical and photochemical stability of NFAs, although they are correlated greatly with the resulting device stability. Herein, we describe a new molecular design strategy to enhance the intrinsic chemical and photochemical stability of acceptor-donor-acceptor (A-D-A)-type NFAs by introducing ring-locked carbon-carbon double bonds between D-A conjugation, attributed to increased steric hindrance of nucleophilic attack and the formation of intramolecular C-H?O interactions. Based on this strategy, two types of NFAs were successfully prepared, 2-(1,1-dicyanomethylene)rhodanine-based IDT-CR and IDTT-CR and thiobarbituric acid-based IDT-CT and IDTT-CT. When blended with a wide-bandgap polymer donor (P3HT), the IDTT-CR-based solar cells can exhibit a PCE of 2.86%. Moreover, a much enhanced PCE of 6.13% was realized by adopting a low-bandgap polymer donor PTB7-Th to pair with IDTT-CT. The fabricated PTB7-Th:IDTT-CT-based OSCs showed very encouraging photostability, the PCE of which could retain >80% of the initial values after 200 h one sun irradiation in air without a UV filter. Such photostability performance has greatly outperformed those from conventional NFAs like ITIC, IT-4F, and IT-M, suggesting the effectiveness of our ring-locking design strategy. Moreover, PTB7-Th:IDTT-CT-based OSCs could retain ～70% of its initial PCE after heating at 85 °C for 100 h. Furthermore, we reported an inferior device stability for P3HT:IDTT-CR based OSCs, which is primarily attributed to the evolution of BHJ film morphology under light illumination.
Diastereo- and Enantioselective Cross-Couplings of Secondary Alkylcopper Reagents with 3-Halogeno-Unsaturated Carbonyl Derivatives
Kremsmair, Alexander,Skotnitzki, Juri,Knochel, Paul
supporting information, p. 11971 - 11973 (2020/09/07)
Chiral secondary alkylcopper reagents were prepared from the corresponding alkyl iodides with retention of configuration by an I/Li-exchange using tBuLi (?100 °C, 1 min) followed by a transmetalation with CuBr?P(OEt)3 (?100 °C, 20 s). These ste
AROMATIC DERIVATIVES, PREPARATION METHODS, AND MEDICAL USES THEREOF
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Paragraph 0162, (2020/09/19)
The present disclosure relates generally to aromatic derivatives that are inhibitors of FGFR4 and are useful in treating FGFR4-associated diseases or conditions. Compositions containing the compounds of the present disclosure are also provided.
Synthesis of Halogenated Cyclic Enamines from Cyclic N-2-En-4-ynyl-N-1-ynylamides and N-Propargyl-N-1-ynylamides via a Tandem Iron Halide Promoted N-to-C Shift-Aza-Prins Cyclization Sequence
Lin, Hsin-Hui,Chiang, Tai-Ching,Wu, Rong-Xuan,Chang, Yi-Mei,Wang, Hao-Wen,Liu, Ssu-Ting,Yeh, Ming-Chang P.
supporting information, (2019/02/07)
A facile and efficient N-to-C allyl shift-aza-Prins cyclization sequence of cyclic N-2-en-4-ynyl-N-1-ynylamides is promoted by iron(III) chloride, generating chloro-containing bridged bicyclic enamines in minutes and in high yields. This reaction involves an unprecedented formation of a ketenimine via Fe(III)-mediated N-to-C allyl rearrangement, followed by aza-Prins cyclization. This sequence can also be applied to the generation of brominated cyclobutenamine derivatives using Fe(III) bromide and N-propargyl-N-1-ynylamides. (Figure presented.).
Palladium-Catalyzed Ullmann Cross-Coupling of β-Iodoenones and β-Iodoacrylates with o-Halonitroarenes or o-Iodobenzonitriles and Reductive Cyclization of the Resulting Products to Give Diverse Heterocyclic Systems
Khan, Faiyaz,Dlugosch, Michael,Liu, Xin,Khan, Marium,Banwell, Martin G.,Ward, Jas S.,Carr, Paul D.
supporting information, p. 2770 - 2773 (2018/05/22)
The palladium-catalyzed Ullmann cross-coupling of β-iodoenones and β-iodoacrylates such as 5 (X = I) with o-halonitroarenes and o-iodobenzonitriles including 2 affords products such as compound 7. These can be engaged in a range of reductive cyclization r
Synthesis method of 3-bromocyclohex-2-enone
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Paragraph 0011, (2017/01/05)
The invention discloses a synthesis method of 3-bromocyclohex-2-enone, and belongs to the technical field of drug intermediate preparation. The synthesis method includes the steps that 1,3-cyclohexanedione, triphenylphosphine and carbon tetrabromide are d
Experimental studies on the selective β-c-h halogenation of enones
Huber, Tatjana,Kaiser, Daniel,Rickmeier, Jens,Magauer, Thomas
, p. 2281 - 2294 (2015/03/18)
Here we describe the realization of a one-pot protocol for the β-C-H halogenation of cyclic enones via umpolung of the β-carbon. The developed method includes hydrazone formation and selective β-halogenation (bromination, chlorination) with N-bromosuccini
Hydrogen-bonding catalysis and inhibition by simple solvents in the stereoselective kinetic epoxide-opening spirocyclization of glycal epoxides to form spiroketals
Wurst, Jacqueline M.,Liu, Guodong,Tan, Derek S.
supporting information; scheme or table, p. 7916 - 7925 (2011/07/08)
Mechanistic investigations of a MeOH-induced kinetic epoxide-opening spirocyclization of glycal epoxides have revealed dramatic, specific roles for simple solvents in hydrogen-bonding catalysis of this reaction to form spiroketal products stereoselectively with inversion of configuration at the anomeric carbon. A series of electronically tuned C1-aryl glycal epoxides was used to study the mechanism of this reaction based on differential reaction rates and inherent preferences for SN2 versus SN1 reaction manifolds. Hammett analysis of reaction kinetics with these substrates is consistent with an SN2 or SN2-like mechanism (ρ = -1.3 vs ρ = -5.1 for corresponding SN1 reactions of these substrates). Notably, the spirocyclization reaction is second-order dependent on MeOH, and the glycal ring oxygen is required for second-order MeOH catalysis. However, acetone cosolvent is a first-order inhibitor of the reaction. A transition state consistent with the experimental data is proposed in which one equivalent of MeOH activates the epoxide electrophile via a hydrogen bond while a second equivalent of MeOH chelates the side-chain nucleophile and glycal ring oxygen. A paradoxical previous observation that decreased MeOH concentration leads to increased competing intermolecular methyl glycoside formation is resolved by the finding that this side reaction is only first-order dependent on MeOH. This study highlights the unusual abilities of simple solvents to act as hydrogen-bonding catalysts and inhibitors in epoxide-opening reactions, providing both stereoselectivity and discrimination between competing reaction manifolds. This spirocyclization reaction provides efficient, stereocontrolled access to spiroketals that are key structural motifs in natural products.
