- DMAP-[2.2]paracyclophane: Observation of an unusual C-C insertion
-
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
- De Rycke, Nicolas,Marrot, Jerome,Couty, Francois,David, Olivier R. P.
-
-
Read Online
- 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
-
(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.
- Ricci, Giacomo,Ruzziconi, Renzo,Giorgio, Egidio
-
-
Read Online
- 5-Deazaflavinocyclophane as a Novel Flavoenzyme Model. Synthesis and Diastereoface-differentiating Reactions
-
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.
- Yanada, Reiko,Higashikawa, Makiko,Miwa, Yoshihisa,Taga, Toru,Yoneda, Fumio
-
-
Read Online
- The synthesis of enantiomerically pure [2.2]paracyclophane derivatives
-
[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
- Rowlands, Gareth J.
-
-
Read Online
- Synthesis of Chiral (R)-4-Hydroxy- and (R)-4-Halogeno[2.2]paracyclophanes and Group Polarizability. Optical Rotation Relationship
-
(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.
- Cipiciani, Antonio,Fringuelli, Francesco,Mancini, Vittorio,Piermatti, Oriana,Pizzo, Ferdinande,Ruzziconi, Renzo
-
-
Read Online
- Diastereoselective Hartwig-Buchwald reaction of chiral amines with rac-[2.2]paracyclophane derivatives
-
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.
- Kreis, Michael,Friedmann, Christian J.,Braese, Stefan
-
-
Read Online
- Diversity-Oriented Synthesis of [2.2]Paracyclophane-derived Fused Imidazo[1,2-a]heterocycles by Groebke-Blackburn-Bienaymé Reaction: Accessing Cyclophanyl Imidazole Ligands Library
-
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.
- Stahlberger, Mareen,Schwarz, Noah,Zippel, Christoph,Hohmann, Jens,Nieger, Martin,Hassan, Zahid,Br?se, Stefan
-
supporting information
(2021/12/13)
-
- Para-Functionalization of N-Substituted 4-amino[2.2]paracyclophanes by Regioselective Formylation
-
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.
- Felder, Simon,Micouin, Laurent,Benedetti, Erica
-
supporting information
p. 4015 - 4018
(2021/05/03)
-
- Chiral fluorescent compound based on cyclophane skeleton and preparation method and application thereof
-
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.
- -
-
Paragraph 0109-0113
(2019/09/14)
-
- A Parylene A precursor synthesis method (by machine translation)
-
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)
- -
-
Paragraph 0027; 0035-0042; 0049-0068
(2018/10/19)
-
- Planar-Chiral [2.2]Paracyclophane-Based Amides as Proligands for Titanium- and Zirconium-Catalyzed Hydroamination
-
A synthetic route to racemic and enantiopure planar chiral [2.2]paracyclophanes with amide groups was developed to combine the well-established reactivity of amides as N,O-chelating ligands in hydroamination reactions with the planar chirality of the [2.2
- Braun, Carolin,Br?se, Stefan,Schafer, Laurel L.
-
supporting information
p. 1760 - 1764
(2017/04/13)
-
- [2.2]Paracyclophanes with N-Heterocycles as Ligands for Mono- and Dinuclear Ruthenium(II) Complexes
-
[2.2]Paracyclophane, with its unique structure, allows the design of unusual 3D structures by functionalization of this rigid and stable hydrocarbon scaffold. Therefore different mono- and homodisubstituted [2.2]paracyclophanes with pyridyl, pyrimidyl and oxazolinyl substituents were developed in order to evaluate their ability as bridging ligands for two ruthenium centres. With the successfully synthesized [2.2]paracyclophane-based N-donor functions, the cycloruthenation reaction using [RuCl2(p-cymene)]2 as precursor was explored. Compared to 2-phenylpyridine, the [2.2]paracyclophane derivative is clearly inferior in the cycloruthenation reaction, resulting in poor yields for the neutral complexes. By addition of KPF6, the cationic complexes can be obtained in good yields and are formed diastereoselectively in case of a pyridyl substituent, resulting in only one diastereomer for dinuclear ruthenium complexes of bispyridyl-substituted [2.2]paracyclophanes as bridging ligands.
- Braun, Carolin,Nieger, Martin,Thiel, Werner R.,Br?se, Stefan
-
supporting information
p. 15474 - 15483
(2017/11/09)
-
- The synthesis of substituted amino[2.2]paracyclophanes
-
Two methodologies for the formation of substituted amino[2.2]paracyclophane derivatives were developed. The first involves the direct amination of bromo[2.2]paracyclophanes with sodium azide. This permits the synthesis of simple mono- and disubstituted de
- Jayasundera, Krishanthi P.,Kusmus, Disra?li N. M.,Deuilhé, Lise,Etheridge, Leonie,Farrow, Zane,Lun, David J.,Kaur, Gurpreet,Rowlands, Gareth J.
-
p. 10848 - 10860
(2016/12/06)
-
- [2-2]PARACYCLOPHANE-DERIVED DONOR/ACCEPTOR-TYPE MOLECULES FOR OLED APPLICATIONS
-
Disclosed are [2.2]paracyclophane-derivative compounds and related polymers that are useful as stable, efficient, blue-light emitting compounds for OLED applications.
- -
-
-
- Chiral [2.2]paracyclophane-based NAC- and NHC-gold(I) complexes Dedicated to Prof. Hubert Schmidbaur on the occasion of his 80th birthday.
-
From enantiomerically pure, planar chiral [2.2]paracyclophane amines a series of nitrogen acyclic carbenegold(I) complexes and nitrogen heterocyclic carbenegold(I) complexes are prepared by a modular template synthesis using isonitriles and amines. These
- G?ker, Verena,Kohl, Simon Robert,Rominger, Frank,Meyer-Eppler, Georg,Volbach, Lucia,Schnakenburg, Gregor,Lützen, Arne,Hashmi, A. Stephen K.
-
-
- Synthesis of planar chiral [2.2]Paracyclophanyl imidazo[1,5-a[pyridinium salts for the rhodium-catalyzed asymmetric arylation
-
Several novel flexibility-restricted imidazo[1,5-a]pyridinium triflates (abbreviated as imidazolium salts) were synthesized from (4S p,13R p)-()-4-amino-13-bromo[2.2]paracyclophane and pyridylaldehyde. These imidazolium salts can be used as nitrogen-containing heterocyclic carbene precursors in asymmetric catalysis and here they are applied in the Rh-catalyzed asymmetric 1,2-addition of arylboronic acids to aldehydes. After optimizing the catalytic situations and testing a series of substrates, moderate enantioselectivity and good yield were obtained.
- Wang, Dengxia,Ma, Yudao,He, Fuyan,Duan, Wenzeng,Zhao, Lei,Song, Chun
-
p. 810 - 825
(2013/02/25)
-
- N-(4-[2.2]paracyclophanyl)-2′-hydroxyacetophenone imine: An effective paracyclophane Schiff-base ligand for use in catalytic asymmetric cyclopropanation reactions
-
The synthesis of planar chiral N-(4-[2.2]paracyclophanyl)-2′- hydroxyacetophenone imine (5) and its use as a ligand for the copper(II) catalyzed cyclopropanation of styrene and stilbene derivatives using diazoesters is presented. Catalyst loadings of 0.1
- Masterson, Douglas S.,Shirley, Caitlyne,Glatzhofer, Daniel T.
-
scheme or table
p. 111 - 115
(2012/08/14)
-
- Planar-chiral imidazole-based phosphine ligands derived from [2.2]paracyclophane
-
Two planar chiral heteroaryl monophosphines have been synthesised and studied. The phosphines are readily prepared from 4-imidazole[2.2]paracyclophane by selective deprotonation and reaction with the appropriate dialkylchlorophosphines. The planar chiral imidazole was constructed in four steps from readily available [2.2]paracyclophane. The 2-phosphino-N-[2.2] paracyclophanes were active in the Suzuki-Miyaura coupling of aryl bromides and chlorides. Coordination studies indicate P,N-chelation in the solid-state. These studies lay the foundations for asymmetric couplings.
- Seacome, Richard J.,Coles, Martyn P.,Glover, Jean E.,Hitchcock, Peter B.,Rowlands, Gareth J.
-
experimental part
p. 3687 - 3694
(2010/06/19)
-
- Towards a flexible strategy for the synthesis of enantiomerically pure [2.2]paracyclophane derivatives: The chemistry of 4-tolylsulfinyl[2.2] paracyclophane
-
The use of enantiomerically enriched 4-tolylsulfinyl[2.2]paracyclophane as a precursor to a variety of mono- and di-substituted [2.2]paracyclophane derivatives is described. The goal of our research is to develop a single general precursor that permits the synthesis of the most common [2.2]paracyclophane substitution patterns. The chemistry of two diastereoisomers of 4-tolylsulfinyl[2.2]paracyclophane has been explored and it facilitates the synthesis of enantiomerically enriched 4-substituted and 4,13-disubstituted [2.2]paracyclophanes. Directed lithiations result in an unusual cyclisation reaction. Whilst the tolyl group cannot realise our goal, the chemistry outlined acts as a successful proof of concept.
- Parmar, Rakesh,Coles, Martyn P.,Hitchcock, Peter B.,Rowlands, Gareth J.
-
experimental part
p. 4177 - 4187
(2011/02/25)
-
- Planar-chiral thioureas as hydrogen-bond catalysts
-
The synthesis of the first enantiopure planar-chiral thiourea catalysts is herewith described. New catalysts 1-3 were applied in asymmetric transformations, such as the FriedelCrafts alkylation of indole, as well as in the transfer hydrogenation of nitroo
- Schneider, Jakob F.,Falk, Florian C.,Froehlich, Roland,Paradies, Jan
-
scheme or table
p. 2265 - 2269
(2010/07/10)
-
- An efficient catalyst system for Pd-catalyzed amination of [2.2]paracyclophanyl bromides
-
(Chemical Equation Presented) Apractical Buchwald-Hartwig amination of [2.2]paracyclophanyl bromides with benzhydrylideneamine is developed. The method provides a facile route to a variety of imino and amino [2.2]paracyclophanes that are otherwise not rea
- Qu, Bo,Ma, Yudao,Ma, Qingshuang,Liu, Xiao,He, Fuyan,Song, Chun
-
supporting information; experimental part
p. 6867 - 6869
(2009/12/30)
-
- Design and synthesis of planar chiral heterocyclic carbene precursors derived from [2.2]paracyclophane
-
(Chemical Equation Presented) A unique family of planar chiral symmetrical N-heterocyclic carbene precursors with restricted flexibility derived from [2.2]paracyclopane were obtained by a new synthetic route. The resolution of 4-amino-13-bromo[2.2]paracyclophane was achieved with relatively high efficiency. Starting from (45p,13Rp)-4-amino-13-bromo[2.2] paracyclophane, the planar chiral pseudogem-disubstituted [2.2]paracyclophanyl dihydroimidazoliums were prepared in a four-step sequence with good yields. The resulting dihydroimidazolium salts were fully characterized with a series of methods including single-crystal X-ray diffraction technique.
- Duan, Wenzeng,Ma, Yudao,Xia, Houqi,Liu, Xueying,Ma, Qingshuang,Sun, Junshan
-
p. 4330 - 4333
(2008/09/21)
-
- The synthesis of enantiomerically pure 4-substituted [2.2]paracyclophane derivatives by sulfoxide-metal exchange
-
A general strategy for the synthesis of enantiomerically pure 4-substituted [2.2]paracyclophanes from a common sulfoxide precursor is described. The Royal Society of Chemistry 2005.
- Hitchcock, Peter B.,Rowlands, Gareth J.,Parmar, Rakesh
-
p. 4219 - 4221
(2007/10/03)
-
- (S)-(-)- and (R)-(+)-4-methyl-2-hydroxymethyl[2]paracyclo-[2](5,8)quinolinophane: Novel N,O-planar chiral catalysts for the enantioselective addition of diethylzinc to aldehydes
-
Novel planar chiral N,O-ligands derived from (R)-(+)and (S)-(-)-2,4-dimethyl[2]paracyclo[2](5,8)quinolinophane were synthesized and employed as catalyst in the enantioselective addition of diethylzinc to aromatic aldehydes. On the basis of the ee values, ranging from 30% to 75%, and the configuration of the obtained 1-phenyl-1-propanols a plausible structure of the transition state for the alkylation process of the aldehydes is discussed.
- Ruzziconi, Renzo,Piermatti, Oriana,Ricci, Giacomo,Vinci, Daniele
-
p. 747 - 750
(2007/10/03)
-
- Synthesis of Amino[2.2]paracyclophanes - Beneficial Monomers for Bioactive Coating of Medical Implant Materials
-
Polymers based on functionalized [2.2]paracyclophanes are interesting interfaces for biomedical applications. A broader application of amino [2.2]paracyclophanes such as 1 and 2 has hitherto been limited by the lack of facile syntheses. Their effective synthesis has now been achieved in a two-step procedure in high yields.
- Lahann, Joerg,Hoecker, Hartwig,Langer, Robert
-
p. 726 - 728
(2007/10/03)
-
- N-Methyl- and N-benzyl-4-amino[2.2]paracyclophanes as unique planar chiral auxiliaries
-
Efficient production of racemic and homochiral N-alkyl-[2.2]paracyclophanes from [2.2]paracyclophane via racemic and homochiral 4-carboxy [2.2]paracyclophane is described, including an excellent procedure for the synthesis of homochiral 4-amino[2.2]paracyclophane. Enolisation followed by electrophilic attack proceeds with diastereoselectivities varying from excellent to modest and the chiral auxiliaries are readily recovered in good yields; the configurational stability of the α-haloamides produced is examined.
- Pelter, Andrew,Kidwell, Huw,Crump, Roger A. N. C.
-
p. 3137 - 3139
(2007/10/03)
-