10122-95-9Relevant academic research and scientific papers
DMAP-[2.2]paracyclophane: Observation of an unusual C-C insertion
De Rycke, Nicolas,Marrot, Jerome,Couty, Francois,David, Olivier R. P.
, p. 1980 - 1984 (2011)
A novel family of nucleophilic catalysts derived from 4-(dimethylamino) pyridine (DMAP) is described. The aminopyridine moiety is attached to a [2.2]paracyclophane skeleton, giving a catalyst with intrinsic planar chirality. Their synthesis is described starting from aminoparacyclophane 5 in four steps. In the course of this preparation, an unprecedented rearrangement involving a C-C bond insertion was observed, leading to an unexpected quinolone-phenyl[2.2] cyclophane (8). The target catalyst 16 was obtained in enantiopure form by formation of diastereomers with a chiral secondary amine, allowing simple chromatographic separation. Preliminary catalytic studies were also performed. Copyright
Atropisomeric (R,R)-2,2′-Bi([2]paracyclo[2](5,8)quinolinophane) and (R,R)-1,1′-Bi([2]paracyclo[2](5,8)isoquinolinophane): Synthesis, structural analysis, and chiroptical properties
Ricci, Giacomo,Ruzziconi, Renzo,Giorgio, Egidio
, p. 1011 - 1018 (2005)
(Chemical Equation Presented) Atropisomeric (R,R)-2,2′-bi([2] paracyclo[2](5,8)quinolinophane) [(R,R)-1] and (R,R)-1,1′-bi([2]- paracyclo[2](5,8)isoquinolinophane) [(R,R)-2] have been prepared in moderate overall yield (17 and 9%, respectively) by a four-step sequence starting from (R)-(-)-4-amino[2.2]paracyclophane and (R)-(-)-4-carboxy[2.2]paracyclophane, respectively. The structures have been determined on the basis of NOE 1H NMR analysis and molecular mechanics (MM) calculations performed with a Spartan02 program, using the MMF94s force field. A preliminary, qualitative analysis of the chiroptical properties of these two compounds has also been attempted. The main spectral data can be interpreted in terms of an almost planar 2,2′-bisquinoline chromophore inserted in a paracyclophane structure in the case of (R,R)-1, while in the case of (R,R)-2, the main role is played by a distorted 1,1′-bisisoquinoline chromophore. On the basis of the above structural results, a hypothesis about the enantioselection capability of these two molecules has also been formulated.
5-Deazaflavinocyclophane as a Novel Flavoenzyme Model. Synthesis and Diastereoface-differentiating Reactions
Yanada, Reiko,Higashikawa, Makiko,Miwa, Yoshihisa,Taga, Toru,Yoneda, Fumio
, p. 1387 - 1390 (1992)
New 5-deazaflavinocyclophane with planar chirality, a novel flavoenzyme model, has been synthesized.This compound provides the first example for selective diastereoface-differentiation during its own reduction and oxidation.
The synthesis of enantiomerically pure [2.2]paracyclophane derivatives
Rowlands, Gareth J.
, p. 1527 - 1534 (2008)
[2.2]Paracyclophane is a fascinating molecule that offers great potential in a wide range of chemical disciplines. Currently, the synthesis of the majority of enantiomerically pure [2.2]paracyclophane derivatives is based on the resolution of a small numb
Synthesis of Chiral (R)-4-Hydroxy- and (R)-4-Halogeno[2.2]paracyclophanes and Group Polarizability. Optical Rotation Relationship
Cipiciani, Antonio,Fringuelli, Francesco,Mancini, Vittorio,Piermatti, Oriana,Pizzo, Ferdinande,Ruzziconi, Renzo
, p. 3744 - 3747 (1997)
(R)-4-Hydroxy-, -4-fluoro-, -4-bromo-, and -4-iodo[2.2]paracyclophanes have been prepared and their absolute configuration assigned on the basis of chemical correlations. Different relationships between the specific optical rotation and the group polarizability have been found depending on the ability of the substituents to conjugate with the aromatic ring. At least for 4,7-disubstituted [2.2]paracyclophanes, the effects of the substituents on the specific rotation seem to be additive, independent of the wavelength used. An equation has been derived which allows to predict, to a satisfactory approximation, the [α] values of 4-X-7-methyl[2.2]paracyclophanes whenever the group polarizability of the substituents is known.
Diastereoselective Hartwig-Buchwald reaction of chiral amines with rac-[2.2]paracyclophane derivatives
Kreis, Michael,Friedmann, Christian J.,Braese, Stefan
, p. 7387 - 7394 (2005)
A Hartwig-Buchwald addition of a variety of chiral amines to rac-4-bromo-[2.2]paracyclophane and rac-trifluoromethanesulfonic acid (4-[2.2]paracyclophane) ester was performed with high diastereoselectivities. Kinetic racemic resolution of the starting materials was achieved, providing a rapid access to enantiomerically enriched 4-bromo-[2.2]paracyclophane and the corresponding enantiomerically pure [2.2]paracyclophane amines. Additionally, the first reaction of a secondary amine with a [2.2]paracyclophane halide was achieved.
Diversity-Oriented Synthesis of [2.2]Paracyclophane-derived Fused Imidazo[1,2-a]heterocycles by Groebke-Blackburn-Bienaymé Reaction: Accessing Cyclophanyl Imidazole Ligands Library
Stahlberger, Mareen,Schwarz, Noah,Zippel, Christoph,Hohmann, Jens,Nieger, Martin,Hassan, Zahid,Br?se, Stefan
supporting information, (2021/12/13)
This report describes the synthesis of a [2.2]paracyclophane-derived annulated 3-amino-imidazole ligand library through a Groebke-Blackburn-Bienaymé three-component reaction (GBB-3CR) approach employing formyl-cyclophanes in combination with diverse aliphatic and aromatic isocyanides and heteroaromatic amidines. The GBB-3CR process gives access to skeletally-diverse cyclophanyl imidazole ligands, namely 3-amino-imidazo[1,2-a]pyridines and imidazo[1,2-a]pyrazines. Additionally, a one-pot protocol for the GBB-3CR by an in situ generation of cyclophanyl isocyanide is demonstrated. The products were analyzed by detailed spectroscopic techniques, and the cyclophanyl imidazo[1,2-a]pyridine was confirmed unambiguously by single-crystal X-Ray crystallography. The cyclophanyl imidazole ligands can be readily transformed to showcase their useful utility in preparing N,C-palladacycles through regioselective ortho-palladation.
Para-Functionalization of N-Substituted 4-amino[2.2]paracyclophanes by Regioselective Formylation
Felder, Simon,Micouin, Laurent,Benedetti, Erica
supporting information, p. 4015 - 4018 (2021/05/03)
Herein, we report a simple and convenient procedure to prepare para-disubstituted [2.2]paracyclophanes in a straightforward manner. Our approach relies on a regioselective formylation of N-substituted 4-amino[2.2]paracyclophanes, which allows an easy access to a series of products incorporating a reactive aldehyde function para to the electron-donating group. These compounds can be engaged in a variety of orthogonal late-stage derivatization processes involving either the carbonyl group or the amine function, and can serve as precursors to rapidly access more complex paracyclophane derivatives. Control of planar chirality is also possible by performing a kinetic resolution of key racemic intermediates through asymmetric transfer hydrogenation. The formylation can be run on a synthetically useful scale, thus confirming the practical applicability of our method.
Chiral fluorescent compound based on cyclophane skeleton and preparation method and application thereof
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Paragraph 0109-0113, (2019/09/14)
The invention relates to a chiral fluorescent compound based on a cyclophane skeleton and a preparation method and application thereof. According to the invention, the cyclophane rigid skeleton structure is utilized, so that the chirality of the cyclophane can be well maintained in an excitation state, and thus high luminous efficiency and good circularly polarized luminous performance (high asymmetry factor) are obtained. The light emission wavelength, circular polarized light emission (CPL) intensity and luminous intensity can be adjusted and controlled by changing R1 and R2 substituents. Bychanging a R3 substituent, molecules are in the state of electron donor/electron acceptor, and a thermally activated delayed fluorescent material can be obtained.
A Parylene A precursor synthesis method (by machine translation)
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Paragraph 0027; 0035-0042; 0049-0068, (2018/10/19)
The invention discloses a Parylene A precursor synthesis method, comprises the following steps: (1) to [2, 2] - to di-methyl benzene ring b body as raw materials through the nitration reaction to obtain the intermediate product 4 - nitro - [2, 2] - dimethyl benzene ring to the second body; (2) the intermediate product 4 - nitro - [2, 2] - dimethyl benzene ring on the second body is arranged in the reactor into the hydrogen in the hydrogenation catalyst under the action of the reduction reaction, to get the crude product, concentrated, recrystallization, dried to obtain 4 - amino - [2, 2] - dimethyl benzene ring on the second body. The mild reaction conditions of the method, the resulting product yield and purity are relatively high, the catalyst and the solvent can be recycled, is suitable for mass production. (by machine translation)
