- Cp*Rh(iii)/boron hybrid catalysis for directed C-H addition to β-substituted α,β-unsaturated carboxylic acids
-
The C-H bond addition reaction of 2-phenylpyridine derivatives with α,β-unsaturated carboxylic acids catalyzed by Cp*Rh(iii)/BH3·SMe2is reported. Activation of C-H bonds with the rhodium catalyst and activation of α,β-unsaturated carboxylic acids with the boron catalyst cooperatively work, and a BINOL-urea hybrid ligand significantly improved the reactivity. With the optimized hybrid catalytic system, various β-disubstituted carboxylic acids were obtained under mild reaction conditions.
- Hirata, Yuki,Kojima, Masahiro,Matsunaga, Shigeki,Tanaka, Ryo,Yoshino, Tatsuhiko
-
supporting information
p. 76 - 79
(2021/12/29)
-
- Chromium-Catalyzed Reductive Cleavage of Unactivated Aromatic and Benzylic C-O Bonds
-
Reductive cleavage of aromatic and benzylic C-O bonds by chromium catalysis is reported. This deoxygenative reaction was promoted by low-cost CrCl 2precatalyst combined with poly(methyl hydrogen siloxane) as the mild reducing agent, providing a strategy in forming reduced motifs by cleavage of unactivated C-O bonds. A range of functional groups such as bromide, chloride, fluoride, hydroxyl, amino, and alkoxycarbonyl can be retained in the reduction.
- Yuan, Shuqing,Ling, Liang,Tang, Jinghua,Luo, Meiming,Zeng, Xiaoming
-
p. 3343 - 3350
(2021/07/02)
-
- Ruthenium-Catalyzed ortho- And meta-H/D Exchange of Arenes
-
Ruthenium-catalyzed aromatic H/D exchange in [D4]acetic acid has been developed. By using N-heteroarenes as directing groups, both ortho and meta positions are selectively deuterated with high levels of D incorporation. Moreover, this strategy provides an alternative way to achieve meta-C-H activation.
- Zhao, Liang-Liang,Liu, Wei,Zhang, Zengyu,Zhao, Hongyan,Wang, Qi,Yan, Xiaoyu
-
supporting information
p. 10023 - 10027
(2019/12/24)
-
- Facile C–H arylation using catalytically active terminal sulfurs of 2 dimensional molybdenum disulfide
-
The first methodology of C–H arylation of heteroarene via 2D transition metal dichalcogenides that have catalytically active edge functional groups was described. The terminal sulfur groups could effectively catalyze a formation of an azo-linked intermediate with aryl diazonium salts, leading to produce heteroarenes with good yields. This novel methodology using bulk 2D transition metal dichalcogenides that have catalytically active edge functional groups can apply for various reactions to achieve C–C bond formation in the fields of heterogeneous catalysis that is easily separable, highly reusable, and inexpensive method.
- Hwang, Eunhee,Mi Lee, Sae,Bak, Sora,Min Hwang, Hee,Kim, Hyunjung,Lee, Hyoyoung
-
supporting information
p. 3969 - 3973
(2018/10/02)
-
- Transition-Metal-Free Decarboxylative Arylation of 2-Picolinic Acids with Arenes under Air Conditions
-
A facile, transition-metal-free, and direct decarboxylative arylation of 2-picolinic acids with simple arenes is described. The oxidative decarboxylative arylation of 2-picolinic acids with arenes proceeds readily via N-chloro carbene intermediates to afford 2-arylpyridines in satisfactory to good yields under transition-metal-free conditions. This new type of decarboxylative arylation is operationally simple and scalable and exhibits high functional-group tolerance. Various synthetically useful functional groups, such as halogen atoms, methoxycarbonyl, and nitro, remain intact during the decarboxylative arylation of 2-picolinic acids.
- Zhang, Xitao,Feng, Xiujuan,Zhou, Chuancheng,Yu, Xiaoqiang,Yamamoto, Yoshinori,Bao, Ming
-
supporting information
p. 7095 - 7099
(2018/11/23)
-
- Ligand-promoted ruthenium-catalyzed: Meta C-H chlorination of arenes using N -chloro-2,10-camphorsultam
-
A practical meta C-H chlorination protocol is established via a Ru(0)-catalyzed ortho-metalation strategy. The use of N-chloro-2,10-camphorsultam as a new chlorinating agent is crucial for the success of the current reaction and an N-heterocyclic carbene (NHC) ligand could significantly enhance the reactivity of the catalytic transformation. The mechanistic studies reveal that an unusual ortho C-H ruthenation relay process with ortho chlorination of the C-Ru bond is probably involved.
- Fan, Zhoulong,Lu, Heng,Cheng, Zhen,Zhang, Ao
-
supporting information
p. 6008 - 6011
(2018/06/18)
-
- Chelation-Assisted Copper-Mediated Direct Acetylamination of 2-Arylpyridine C-H Bonds with Cyanate Salts
-
In this study, the coupling of 2-phenylpyridine derivatives and potassium cyanate through C-H bond functionalization in the presence of a copper salt is developed for the first time. By this protocol, various heteroarylated acetanilide derivatives are synthesized in good yields. 2-Phenylpyridines containing electron-donating and -withdrawing groups appear to be well-tolerated by this transformation.
- Kianmehr, Ebrahim,Amiri Lomedasht, Yousef,Faghih, Nasser,Khan, Khalid Mohammed
-
p. 6087 - 6092
(2016/07/23)
-
- Cobalt(III)-Catalyzed Directed C-H Coupling with Diazo Compounds: Straightforward Access towards Extended π-Systems
-
The first highly efficient and scalable cobalt-catalyzed directed C-H functionalization with carbene precursors is presented. This methodology provides a modular route towards a new class of conjugated polycyclic hydrocarbons with tunable emission wavelengths both in solution and in the solid state.
- Zhao, Dongbing,Kim, Ju Hyun,Stegemann, Linda,Strassert, Cristian A.,Glorius, Frank
-
supporting information
p. 4508 - 4511
(2015/04/14)
-
- RhIII-Catalyzed C-H Activation with Pyridotriazoles: Direct Access to Fluorophores for Metal-Ion Detection
-
The first C-H bond activation with pyridotriazoles as coupling partners is presented using a RhIII catalyst. The pyridotriazoles can be used as new carbene precursors in C-H activation for direct access to novel fluorescent scaffolds. These tunable fluorophores can be applied for the detection of metal ions.
- Kim, Ju Hyun,Gensch, Tobias,Zhao, Dongbing,Stegemann, Linda,Strassert, Cristian A.,Glorius, Frank
-
supporting information
p. 10975 - 10979
(2015/09/15)
-
- Triarylbismuthanes as threefold aryl-transfer reagents in regioselective cross-coupling reactions with bromopyridines and quinolines
-
Cross-coupling studies using bromopyridines and bromoquinolines with triarylbismuths as threefold coupling reagents in substoichiometric amounts under Pd-catalysed conditions are disclosed. The reactivity was high with both mono- and dibromopyridyl substrates, and mono- and bis-couplings were carried out regioselectively. A library of monoaryl and diaryl pyridines was formed in high yields. A one-pot strategy provided a simple and straightforward synthesis of both symmetrical and unsymmetrical diarylpyridines. Arylations of 2-bromo- and 3-bromoquinolines were achieved with triarylbismuth reagents. This study demonstrates that triarylbismuths may be used as threefold arylating reagents for the synthesis of aryl pyridines and quinolines through couplings with bromopyridines and bromoquinolines under Pd-catalysed conditions. Copyright
- Rao, Maddali L.N.,Dhanorkar, Ritesh J.
-
supporting information
p. 5214 - 5228
(2014/10/15)
-
- Direct arylation of pyridines without the use of a transition metal catalyst
-
A method for achieving the direct arylation of pyridines with phenylhydrazine hydrochloride was developed in this study. This new reaction proceeds readily at room temperature without the use of any transition metal catalysts. This method allows rapid access to various arylated heterocycles that are more difficult to access through traditional methods.
- Li, Yahui,Liu, Wei,Kuang, Chunxiang
-
supporting information
p. 7124 - 7127
(2014/07/07)
-
- Copper-catalyzed direct C-H arylation of pyridine N-oxides with arylboronic esters: One-pot synthesis of 2-arylpyridines
-
The first example of the copper-catalyzed direct C-H arylation of pyridine N-oxides with arylboronic esters has been developed, leading to a wide range of 2-arylpyridines in a one-pot synthesis with moderate to good yields without an additional reductant. This transformation allows for rapid access to a variety of 2-arylpyridines using an inexpensive catalytic system that would be more difficult to access with traditional methods. Thus, this method represents a simple and practical procedure to access 2-arylpyridines.
- Shen, Yan,Chen, Jiuxi,Liu, Miaochang,Ding, Jinchang,Gao, Wenxia,Huang, Xiaobo,Wu, Huayue
-
supporting information
p. 4292 - 4295
(2014/04/17)
-
- Pd(0)-catalyzed Cu(I)-thiophene-2-carboxylate-mediated cross-coupling of heteroaromatic thioethers and boronic acids - First Liebeskind-Srogl reaction in water
-
The first example of a Liebeskind-Srogl cross-coupling reaction in water as sole reaction solvent is reported. 2-(Methylthio)pyridine and 2-(methylthio)benzothiazole were reacted in the presence of a Pd(0) catalyst and copper(I) thiophene-2-carboxylate with a series of arylboronic acids. These cross coupling reactions in water proceeded well with electron-rich boronic acids and gave comparable yields to literature examples using organic solvents. Electron-poor boronic acids gave somewhat lower yields in aqueous medium.
- Koley, Moumita,Wimmer, Laurin,Schnuerch, Michael,Mihovilovic, Marko D.
-
p. 1368 - 1373
(2014/01/06)
-
- A highly active and general catalyst for the stille coupling reaction of unreactive aryl, heteroaryl, and vinyl chlorides under mild conditions
-
A β-diketiminatophosphane-palladium complex was found to act as an efficient and general catalyst in the Stille coupling reaction of various aryl and heteroaryl chlorides with organostannanes. The results show that this catalytic system allows for the use of less reactive substrates such as deactivated or sterically hindered aryl chlorides. A catalyst loading of 0.5 mol% was sufficient to achieve excellent performance under relatively mild reaction conditions. Furthermore, the scope of catalyst was extended to the coupling of vinyl chlorides. Copyright
- Lee, Dong-Hwan,Qian, Yingjie,Park, Ji-Hoon,Lee, Jong-Suk,Shim, Sang-Eun,Jin, Myung-Jong
-
supporting information
p. 1729 - 1735
(2013/07/19)
-
- Pd(II)-catalyzed phosphorylation of aryl C-H bonds
-
A Pd(II)-catalyzed C-H phosphorylation reaction has been developed using heterocycle-directed ortho-palladation. Both H-phosphonates and diaryl phosphine oxides are suitable coupling partners for this reaction.
- Feng, Chen-Guo,Ye, Mengchun,Xiao, Kai-Jiong,Li, Suhua,Yu, Jin-Quan
-
supporting information
p. 9322 - 9325
(2013/07/19)
-
- Pyridine-directed palladium-catalyzed phosphonation of C(sp2)-H bonds
-
Follow the guide: The palladium-catalyzed phosphonation of a C(sp 2)-H bond occurs through the use of a pyridyl group as the directing group. α-Hydroxyalkylphosphonate is used as the phosphonating reagent (see scheme). Copyright
- Li, Changkun,Yano, Takaaki,Ishida, Naoki,Murakami, Masahiro
-
supporting information
p. 9801 - 9804
(2013/09/23)
-
- Reductive cleavage of the Csp2-Csp3 bond of secondary benzyl alcohols: Rhodium catalysis directed by N-containing groups
-
Cutting loose: 1,1-Biarylmethanol substrates undergo reductive cleavage of the C-C bond in the presence of a cationic RhIII catalyst and H 2 (see scheme; DG=directing group). Various functional groups are tolerated in the reaction system. Preliminary studies indicate that a five-membered rhodacycle intermediate, which then converts into a Rh III hydride species for the reduction, is involved in the catalytic cycle. Copyright
- Chen, Kang,Li, Hu,Lei, Zhi-Quan,Li, Yang,Ye, Wen-He,Zhang, Li-Sheng,Sun, Jian,Shi, Zhang-Jie
-
supporting information
p. 9851 - 9855
(2012/11/07)
-
- Rh-catalyzed C-C cleavage of benzyl/allylic alcohols to produce benzyl/allylic amines or other alcohols by nucleophilic addition of intermediate rhodacycles to aldehydes and imines
-
We report three transformations: 1) direct transformation from biarylmethanols into biarylmethylamines; 2) direct transformation from one biarylmethanol into another biarylmethanol; 3) direct transformation from allylic alcohols into allylic amines. These transformations are based on pyridyl-directed Rh-catalyzed C-C bond cleavage of secondary alcohols and subsequent addition to C=X (X=N or O) double bonds. The reaction conditions are simple and no additive is required. The driving force of C-C bond cleavage is the formation of the stable rhodacycle intermediate. Other directing groups, such as the pyrazolyl group, can also be used although it is not as efficient as the pyridyl group. We carried out in-depth investigations for transformation 1 and found that: 1) the substrate scope was broad and electron-rich alcohols and electron-deficient imines are more efficient; 2) as the leaving group, aldehyde had no significant impact on either the C-C bond cleavage or the whole transformation; 3) mechanistic studies (intermediate isolation, in situ NMR spectroscopic studies, competing reactions, isotopic labeling experiments) implied that: i) The C-C cleavage was very efficient under these conditions; ii) there is an equilibrium between the rhodacycle intermediate and the protonated byproduct phenylpyridine; iii) the addition step of the rhodacycle intermediate to imines was slower than the C-C cleavage and the equilibrium between the rhodacycle and phenylpyridine; iv) the whole transformation was a combination of two sequences of C-C cleavage/nucleophilic addition and C-C cleavage/protonation/C-H activation/nucleophilic addition, with the latter being perhaps the main pathway. We also demonstrated the first example of cleavage of an C(alkenyl)-C(benzyl) bond. These transformations showed the exchange (or substitution) of the alcohol group with either an amine or another alcohol group. Like the "group transplant", this method offers a new concept that can be used to directly synthesize the desired products from other chemicals through reorganization of carbon skeletons.
- Zhang, Xi-Sha,Li, Yang,Li, Hu,Chen, Kang,Lei, Zhi-Quan,Shi, Zhang-Jie
-
supporting information
p. 16214 - 16225
(2013/02/21)
-
- Ring-closing metathesis approach to heteroaromatic cations: Synthesis of benzo[a]quinolizinium salts
-
Benzo[a]quinolizinium salts have been synthesized through ring-closing metathesis reactions of 1-butenyl-2-vinylisoquinolinium, 2-butenyl-1- vinylisoquinolinium and 2-styryl-1-vinylpyridinium salts in the presence of Grubbs andHoveyda-Grubbs catalysts. Th
- Nunez, Ana,Abarca, Beatriz,Cuadro, Ana M.,Alvarez-Builla, Julio,Vaquero, Juan J.
-
scheme or table
p. 1280 - 1290
(2011/04/17)
-
- Highly luminescent tridentate NC*N platinum(II) complexes featured in fused five-six-membered metallacycle and diminishing concentration quenching
-
A series of cyclometalating ligands, N-phenyl-N-(3-(pyridin-2-yl)phenyl) pyridin-2-amine (L1), N-(3-(1H-pyrazol-1-yl)phenyl)-N-phenylpyridin-2-amine (L2), N-phenyl-N-(3-(quinolin-2-yl)phenyl)pyridin-2-amine (L3), N-phenyl-N-(3-(pyridin-2-yl)phenyl)quinolin-2-amine (L4), N-(3-(isoquinolin-1- yl)phenyl)-N-phenylpyridin-2-amine (L5), and N-phenyl-N-(3-(pyridin-2-yl)phenyl) isoquinolin-1-amine (L6), were synthesized, which reacted with K 2PtCl4 in glacial acetic acid to produce NC*N-coordinated platinum(II) complexes featured in a fused five-six-membered metallacycle, 1-6, respectively. The structures of 1, 3, 4, and 6 were determined by single crystal X-ray crystallography. The square geometries of the complexes are improved when compared with those of the N^C^N-coordinated complexes as the bite angles for the platinum in N^C*N-coordinated complexes 1, 3, and 4 are increased. The Pt-C bonds (1.94-1.95 A) are shorter than those of C^N^N-coordinated platinum complexes but longer than those found for N^C^N-coordinated platinum complexes. With the increase of the steric interaction, the distortion of the molecules from a planar coordination geometry becomes more and more severe from 1 to 3 to 4 and 6, and in 6, the N-phenyl ring has to stand up on the coordination sphere to minimize the steric interaction with the N-isoquinolyl ring. The photophysical properties of the complexes were studied, and their absorption and emission spectra were interpreted by relating to the structural features revealed by the X-ray crystal structures and the orbital characters predicted by DFT calculations. All complexes are emissive in fluid at room temperature, and the quantum yields (up to 0.65) are comparable to those of highly emissive N^C^N-coordinated platinum complexes. Self-quenching was not observed in the concentration range of 10-6 to 10-4 M. Large rigidochromic shifts for the emissions of 2, 4, and 6 upon cooling from room temperature to rigid glass (77 K) were observed. Two different triplet states that control the emissions were proposed to account for the photophysical properties of 6.
- Vezzu, Dileep A. K.,Ravindranathan, Deepak,Garner, Alexander W.,Bartolotti, Libero,Smith, Meredith E.,Boyle, Paul D.,Huo, Shouquan
-
experimental part
p. 8261 - 8273
(2011/10/10)
-
- Pd(II)-Catalyzed ortho-trifluoromethylation of arenes using TFA as a promoter
-
"Chemical equation presented" A Pd(II)-catalyzed C-H activation/trifluoromethylation of arenes with an electrophilic trifluoromethylation reagent using diverse heterocycle directing groups is reported. The presence of trifluoroacetic acid is crucial for this catalytic reaction.
- Wang, Xisheng,Truesdale, Larry,Yu, Jin-Quan
-
supporting information; experimental part
p. 3648 - 3649
(2010/05/15)
-
- Synthesis of Vinylphenylpyridine and Living Anionic Polymerization
-
Provided are a vinyl-biphenylpyridine monomer and a polymer thereof. More particularly, the present invention provides a vinyl-biphenylpyridine monomer having a side chain of pyridine or phenylpyridine as a functional group, a homopolymer of which molecul
- -
-
Page/Page column 7
(2009/05/29)
-
- SYNTHESIS OF VINYLPHENYLPYRIDINE AND LIVING ANIONIC POLYMERIZATION
-
Provided are a vinyl-biphenylpyridine monomer and a polymer thereof. More particularly, the present invention provides a vinyl-biphenylpyridine monomer having a side chain of pyridine or phenylpyridine as a functional group, a homopolymer of which molecul
- -
-
Page/Page column 10
(2010/11/29)
-
- Palladium-N-heterocyclic carbene an efficient catalytic system for the carbonylative cross-coupling of pyridine halides with boronic acids
-
Carbonylative cross-coupling of different pyridyl halides with various boronic acids was studied using catalytic systems constituted of N-heterocyclic carbene type ligands and palladium. These systems easily obtained in situ from the corresponding imidazolium salt and palladium acetate appear more efficient toward bromopyridines than catalysts based on hindered and basic alkylphosphines such as tricyclohexylphosphine. Their higher efficiency was also evidenced by coupling using chloro- or dichloropyridines and chloroquinolines, which practically do not react with catalytic systems based on phosphines.
- Maerten, Eddy,Sauthier, Mathieu,Mortreux, André,Castanet, Yves
-
p. 682 - 689
(2007/10/03)
-
- Platinum complex and light-emitting device
-
A platinum complex represented by the general formula 1, useful as a phosphorescence emission material, a tetradentate ligand useful for synthesizing the platinum complex, and a light-emitting device containing at least one of the platinum complex. In the
- -
-
Page/Page column 30-31
(2010/11/23)
-
- PLATINUM COMPLEX AND LUMINESCENT ELEMENT
-
Provision of a novel platinum complex which is useful as a material for a light-emitting device of good light emission characteristic and light emission efficiency, and a novel light-emitting material that may be utilized in various fields. A platinum complex represented by the following general formula (1): (in which two rings of ring A, ring B, ring C, and ring D represent nitrogen-containing heterocyclic rings which may have a substituent and the remaining two rings of them represent aryl rings or hetero aryl rings which may have a substituent, the ring A and the ring B, the ring A and the ring C or/and the ring B and the rind D may form condensed rings. Two of X1, X2, X3, and X4 represent nitrogen atoms coordination bonded to a platinum atom and the remaining two of them represent carbon atoms or nitrogen atoms. Q1, Q2, and Q3 each represents a bond, oxygen atom, sulfur atom or bivalent group, two of Z1, Z2, Z3, and Z4 represent coordination bonds, and the remaining two of them represent covalent bonds, oxygen atoms or sulfur atoms), and a light-emitting device containing the platinum complex.
- -
-
Page/Page column 20
(2008/06/13)
-
- Photo-Arylation. IV. Synthesis of 2-Arylpyridines by Photo-Reaction of 2-Iodopyridine with Substituted Benzenes
-
Photolysis of a mixture of 2-iodopyridine and a variety of substituted benzenes in dichloromethane afforded the corresponding 2-arylpyridines as isomeric mixtures.Based on the isomer distributions of the products and the formation of 2-chloropyridine as a by-product, the reactivity of 2-iodopyridine in the present reaction was suggested to be electrophilic in character.Keywords - arylpyridine; 2-pyridinylation; photo-arylation; photolysis; 2-iodopyridine; homolytic aromatic substitution
- Terashima, Masanao,Seki, Koh-ichi,Yoshida, Chihiro,Ohkura, Kazue,Kanaoka, Yuichi
-
p. 1009 - 1015
(2007/10/02)
-