- Self-activation and 1,8-stereoinduction in a boronate-substituted dienophile
-
The [4+2] cycloaddition of ortho-boronoanilide dienophile 4 with cyclopentadiene was found to proceed faster than both its para isomer 8 and the unsubstituted derivative 6, thereby confirming that self-activation by internal coordination is operative in the case of 4. Chiral boronic esters derivatives 9 and 10 provided a small level of remote 1,8-stereoinduction. These results show that dialkoxyboronic esters can operate as weak, internal Lewis acids and activate carbonyl-containing functionalities in cycloaddition reactions.
- Kennedy, Jason W. J.,Hall, Dennis G.
-
-
Read Online
- Photoinitiated long-lived charge separation with near-unity quantum yield in donor-acceptor1-acceptor2 systems for artificial photosynthesis
-
We report the synthesis and photophysical characterization of isomeric donor-acceptor1-acceptor2 (D-A1-A2) triads each comprising a perylene donor (D) connected by a xylene bridge to a naphthalene-1,8-dicarboximide primary acceptor (NMI, A1) that is, in turn, covalently linked to a naphthalene-1,4:5,8-bis(dicarboximide) secondary acceptor (NDI, A2) through a benzene ring at its ortho, meta or para positions (Per-Xy-NMI-x-NDI). Selective photoexcitation of Per produces both Per+? and NDI?? simultaneously with time constants of ～50 ps in benzonitrile and ～80 ps in toluene with a >98% yield. This is much faster than expected for single-step electron transfer from 1*Per to NDI and is consistent with a two-step mechanism, 1*Per-Xy-NMI-x-NDI → Per+?-Xy-NMI??-x-NDI → Per+?-Xy-NMI-x-NDI??, in which the second step is much faster than the first step. In addition, preserving long-lived charge separation in these systems is found to depend on inhibiting charge recombination by a triplet radical ion pair recombination pathway.
- Han, Won-Sik,Veldkamp, Brad S.,Dyar, Scott M.,Eaton, Samuel W.,Wasielewski, Michael R.
-
-
Read Online
- 1,3,5-Tris(2′-aminophenyl)benzene: A novel platform for molecular receptors
-
The synthesis of a novel, rigid, aromatic platform for molecular receptors is described. 1,3,5-Tris(2′-aminophenyl)benzene was prepared via Suzuki-Miyaura cross-coupling reactions of 2-aminophenylboronic acid with 1,3,5-triiodobenzene in the presence of Ba(OH)2, Pd(OAc)2 and (2-biphenyl)dicyclohexylphosphine. Alternatively, one-pot borylation of 2-bromoaniline and cross-coupling of the resulting boronate ester with 1,3,5-triiodobenzene was investigated. Georg Thieme Verlag Stuttgart.
- Pia?tek, Piotr,S?omiany, Norbert
-
-
Read Online
- Recyclable Pd2dba3/XPhos/PEG-2000 System for Efficient Borylation of Aryl Chlorides: Practical Access to Aryl Boronates
-
Pd2dba3/XPhos in poly(ethylene glycol) (PEG-2000) is shown to be a highly stable and efficient catalyst for the borylation of aryl chlorides with bis(pinacolato)diboron. The borylation reaction proceeds smoothly at 110 °C, delivering a wide variety of aryl boronates in good to excellent yields with high functional group tolerance. The crude products were easily isolated via simple extraction of the reaction mixture with cyclohexane. Moreover, both expensive Pd2dba3 and XPhos in PEG-2000 system could be readily recycled and reused more than six times without loss of catalytic efficiency.
- Cai, Mingzhong,Huang, Bin,Luo, Chengkai,Xu, Caifeng
-
-
- Enantioselective Construction of Axially Chiral Azepine-Containing P,N-Ligands from l -Alanine
-
A family of axially chiral azepine-containing seven-membered cyclic P,N-ligands (named Indole-azepinap) have been prepared by using l-alanine as an original chirality source. The direct chromatographic separation of two diastereomeric phosphine oxides on silica gel enabled these ligands to be easy available, allowing further structural and electronic modifications. Preliminary application of these Indole-azepinaps has been demonstrated in a Pd-catalyzed asymmetric allylic alkylation with high yields and moderate enantioselectivities.
- Zhang, Jinlong,Gao, Zeng,Qian, Jinlong,Yang, Huameng,He, Maosheng,Jiang, Gaoxi
-
supporting information
p. 7814 - 7818
(2021/10/20)
-
- Cross-Coupling through Ag(I)/Ag(III) Redox Manifold
-
In ample variety of transformations, the presence of silver as an additive or co-catalyst is believed to be innocuous for the efficiency of the operating metal catalyst. Even though Ag additives are required often as coupling partners, oxidants or halide scavengers, its role as a catalytically competent species is widely neglected in cross-coupling reactions. Most likely, this is due to the erroneously assumed incapacity of Ag to undergo 2e? redox steps. Definite proof is herein provided for the required elementary steps to accomplish the oxidative trifluoromethylation of arenes through AgI/AgIII redox catalysis (i. e. CEL coupling), namely: i) easy AgI/AgIII 2e? oxidation mediated by air; ii) bpy/phen ligation to AgIII; iii) boron-to-AgIII aryl transfer; and iv) ulterior reductive elimination of benzotrifluorides from an [aryl-AgIII-CF3] fragment. More precisely, an ultimate entry and full characterization of organosilver(III) compounds [K]+[AgIII(CF3)4]? (K-1), [(bpy)AgIII(CF3)3] (2) and [(phen)AgIII(CF3)3] (3), is described. The utility of 3 in cross-coupling has been showcased unambiguously, and a large variety of arylboron compounds was trifluoromethylated via [AgIII(aryl)(CF3)3]? intermediates. This work breaks with old stereotypes and misconceptions regarding the inability of Ag to undergo cross-coupling by itself.
- Demonti, Luca,Mézailles, Nicolas,Nebra, Noel,Saffon-Merceron, Nathalie
-
supporting information
p. 15396 - 15405
(2021/10/12)
-
- Oxidation of Nonactivated Anilines to Generate N-Aryl Nitrenoids
-
A low-temperature, protecting-group-free oxidation of 2-substituted anilines has been developed to generate an electrophilic N-aryl nitrenoid intermediate that can engage in C-NAr bond formation to construct functionalized N-heterocycles. The exposure of 2-substituted anilines to PIFA and trifluoroacetic acid or 10 mol percent Sc(OTf)3 triggers nitrenoid formation, followed by productive and selective C-NAr and C-C bond formation to yield spirocyclic- or bicyclic 3H-indoles or benzazepinones. Our experiments demonstrate the breadth of these oxidative processes, uncover underlying fundamental elements that control selectivity, and demonstrate how the distinct reactivity patterns embedded in N-aryl nitrenoid reactive intermediates can enable access to functionalized 3H-indoles or benzazepinones.
- Deng, Tianning,Mazumdar, Wrickban,Ford, Russell L.,Jana, Navendu,Izar, Ragda,Wink, Donald J.,Driver, Tom G.
-
supporting information
p. 4456 - 4463
(2020/03/05)
-
- I(III)-catalyzed oxidative cyclization - Migration tandem reactions of unactivated anilines
-
An I(III)-catalyzed oxidative cyclization-migration tandem reaction using Selectfluor as the oxidant was developed that converts unactivated anilines into 3H-indoles is reported herein. The reaction requires as little as 1 mol % of the iodocatalyst and is mild, tolerating pyridine and thiophene functional groups, and the dependence of the diastereoselectivity of the process on the identity of the iodoarene or iodoalkane precatalyst suggests that the catalyst is present for the stereochemical determining C-N bond forming step.
- Deng, Tianning,Shi, Emily,Thomas, Elana,Driver, Tom G.
-
supporting information
p. 9102 - 9106
(2020/11/13)
-
- Influence of meso-linker attachment on the formation of coreπ interactions in urea-functionalized porphyrins
-
The ability to cover the face of a porphyrin macrocycle selectively is an attractive feature for concepts such as catalysis and anion binding that is reliant on porphyrin core interactions. Herein, we have synthesized a family of mono-urea functionalized porphyrin complexes with intent to investigate their potential to form coreπ interactions selectively to one face of the porphyrin macrocycle. By altering the distance between the urea moiety and the porphyrin through direct linkage or introducing a linker group we can control the formation of the core interactions. This is clearly seen in the crystal structure of 1-phenyl-3-(2-([10,15,20-triphenylporphyrinato]zinc(II)-5-yl)phenyl)urea where a unique face capping effect is demonstrated. In the crystal of this complex, there is a hydrogen-bonding network between the urea group and the axial methanol ligand forming head-to-tail aggregates with the Zn-O axis all molecules pointing in one direction.
- Flanagan, Keith J.,Ryan, Aoife A.,Twamley, Brendan,Senge, Mathias O.
-
p. 755 - 764
(2020/09/02)
-
- Ruthenium-catalyzed regio- And site-selective: Ortho C-H borylation of phenol derivatives
-
Efficient synthesis of o-borylphenols is achieved through the Ru-catalyzed regio- and site-selective sp2 C-H borylation of aryl diphenylphosphinites followed by removal of the phosphorus directing group. A successful application to aryl phosphites enables practical one-pot borylation of phenols, demonstrating high synthetic utility of this protocol.
- Homma, Yuki,Fukuda, Kazuishi,Iwasawa, Nobuharu,Takaya, Jun
-
supporting information
p. 10710 - 10713
(2020/10/02)
-
- Synthesis method of 2-nitrophenylboronic acid pinacol ester
-
The invention relates to a synthetic method of 2-nitrophenylboronic acid pinacol ester, and belongs to the field of synthesis of medical intermediates. Nitrobenzene is used as a raw material and reacts with BCl3 or BBr3 under the catalysis of a catalyst B(C6F5)3 for ortho-orientation, pinacol is added, and the 2-nitrophenylboronic acid pinacol ester is generated under the alkaline condition. According to the method, a common reaction raw material is adopted, selective guiding is carried out under mild conditions, high-purity 2-nitrophenylboronic acid pinacol ester can be obtained through recrystallization of a crude product, 2-aminobenzene boronic acid pinacol ester can be obtained through continuous catalytic hydrogenation, and the defects that in a traditional method, raw material is noteasy to obtain, danger is high, and ultralow temperature or precious metal is needed for use are overcome.
- -
-
-
- Copper-Photocatalyzed Borylation of Organic Halides under Batch and Continuous-Flow Conditions
-
The copper-photocatalyzed borylation of aryl, heteroaryl, vinyl and alkyl halides (I and Br) was reported. The reaction proceeded using a new heteroleptic Cu complex under irradiation with blue LEDs, giving the corresponding boronic-acid esters in good to excellent yields. The reaction was extended to continuous-flow conditions to allow an easy scale-up. The mechanism of the reaction was studied and a mechanism based on a reductive quenching (CuI/CuI*/Cu0) was suggested.
- Nitelet, Antoine,Thevenet, Damien,Schiavi, Bruno,Hardouin, Christophe,Fournier, Jean,Tamion, Rodolphe,Pannecoucke, Xavier,Jubault, Philippe,Poisson, Thomas
-
supporting information
p. 3262 - 3266
(2019/02/13)
-
- Achieving High Ortho Selectivity in Aniline C-H Borylations by Modifying Boron Substituents
-
High ortho selectivity for Ir-catalyzed C-H borylations (CHBs) of anilines results when B2eg2 (eg = ethylene glycolate) is used as the borylating reagent in lieu of B2pin2, which is known to give isomeric mixtures with anilines lacking a blocking group at the 4-position. With this modification, high selectivities and good yields are now possible for various anilines, including those with groups at the 2- and 3-positions. Experiments indicate that ArylN(H)Beg species are generated prior to CHB and support the improved ortho selectivity relative to B2pin2 reactions arising from smaller Beg ligands on the Ir catalyst. The lowest-energy transition states (TSs) from density functional theory computational analyses have N-H···O hydrogen-bonding interactions between PhN(H)Beg and O atoms in Beg ligands. Ir-catalyzed CHB of PhN(H)Me with B2eg2 is also highly ortho-selective. 1H NMR experiments show that N-borylation fully generates PhN(Me)Beg prior to CHB. The TS with the lowest Gibbs energy was the ortho TS, in which the Beg unit is oriented anti to the bipyridine ligand.
- Smith, Milton R.,Bisht, Ranjana,Haldar, Chabush,Pandey, Gajanan,Dannatt, Jonathan E.,Ghaffari, Behnaz,Maleczka, Robert E.,Chattopadhyay, Buddhadeb
-
p. 6216 - 6223
(2018/05/23)
-
- Room-temperature borylation and one-pot two-step borylation/Suzuki-Miyaura cross-coupling reaction of aryl chlorides
-
A highly efficient room-temperature borylation strategy of aryl chlorides is described. Utilizing Buchwald's second-generation preformed catalyst, boronate esters were obtained for a wide range of substrates in high yield. The method was also applied to Suzuki-Miyaura cross-coupling reaction in a one-pot two-step sequential manner, providing a facile and convenient access to the direct synthesis of biaryl compounds from aryl chlorides.
- Ji, Hong,Wu, Li-Yang,Cai, Jiang-Hong,Li, Guo-Rong,Gan, Na-Na,Wang, Zhao-Hua
-
p. 13643 - 13648
(2018/04/24)
-
- Synthesis method of phosphorescent materials of homoleptic Ir complex including DMP ligands using microwave
-
The present invention relates to a synthesis method capable of synthesizing an iridium compound based on dimethylphenyl (DMP) ligand with high yield and excellent process efficiency. More specifically, the present invention relates to a synthesis method which applies a microwave reactor and is capable of securing significantly improved yields over previously known yields using an iridium dimer structure during a reaction.COPYRIGHT KIPO 2018
- -
-
Paragraph 0182; 0183; 0199-0201; 0225; 0226; 0243-0245; 0268
(2018/06/28)
-
- Palladium-Catalyzed Regioselective Synthesis of 3-Arylindoles from N-Ts-Anilines and Styrenes
-
A Pd-catalyzed intermolecular oxidative annulation between N-Ts-anilines and styrenes was developed. This method offers a straightforward and robust approach to a wide range of 3-arylindoles using readily available starting materials with good functional-group tolerance and high regioselectivity and efficiency. Further elaboration of the products obtained from this process provided access to highly functionalized and structurally diverse indoles, for example, 3-(indol-3-yl)carbazoles, 1,9-dihydropyrrolo-[2,3-b]carbazoles, and 3′-aryl-3,5′-biindoles.
- Youn, So Won,Ko, Tae Yun,Jang, Young Ho
-
supporting information
p. 6636 - 6640
(2017/05/29)
-
- Protein kinase inhibitor and its composition and use thereof
-
The invention relates to compounds as shown in the general formula (I), pharmaceutical compositions containing the compounds, a method for treating diseases and disease symptoms related to abnormal activity of protein kinase by using the compounds, and medicinal use of the compounds.
- -
-
Paragraph 0474-0476
(2017/08/02)
-
- A synthetic amino acid frequency that alcohol ester
-
The invention relates to a method of synthesizing aminophenylboronic acid pinacol ester. The method includes subjecting bromoaniline having different substitute positions to silanization protection, reacting with magnesium metal or butyl lithium, and performing boronization/deprotection/esterification to obtain a product. Raw materials and agents, which are adopted in the method, are cheap and easily available. Reaction conditions are mild. Only simple treatment is needed after a reaction in each step is finished. The method is capable of continuous operation. The total yield is 40-55%. The purity of the product is high. The method is suitable for large-scale amplification production.
- -
-
-
- Radical Metal-Free Borylation of Aryl Iodides
-
A simple metal-free borylation of aryl iodides mediated by a fluoride sp 2 -sp 3 diboron adduct is described. The reaction conditions are compatible with various functional groups. Electronic effects of substituents do not affect the borylation while steric hindrance does. The reaction proceeds via a radical mechanism in which pyridine serves to stabilize the boryl radicals, generated in situ.
- Pinet, Sandra,Liautard, Virginie,Debiais, Mégane,Pucheault, Mathieu
-
p. 4759 - 4768
(2017/10/03)
-
- COMPOUND FOR ORGANIC ELECTROLUMINESCENT DEVICE AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
-
This invention provides a compound for an organic electroluminescent device and an organic electroluminescent device including the same. This invention provides a compound for an organic EL device, which may have high thermal stability, improved light emission efficiency and lifetime and hole transport capability. Further, when this compound is used as a hole transport layer material in contact with a light emitting layer, thereby increasing a triplet energy, ultimately improving efficiency of the organic EL device and lifetime.
- -
-
Paragraph 197; 198; 199; 200
(2017/12/01)
-
- Discovery of 2-(pyridin-2-yl)aniline as a directing group for the sp2 C-H bond amination mediated by cupric acetate
-
2-(Pyridin-2-yl) aniline was designed as a new, removable directing group in promoting C-H amination mediated by cupric acetate. Employing this auxiliary, the β-C(sp2)-H bonds of benzamide derivatives can be effectively aminated with a variety of amines in moderate to good yields with good functional group tolerance in air. In addition, the quinazolinone derivatives were isolated from the reaction mixture of N-(2-(pyridin-2-yl)phenyl)benzamide with formamide or 5-nitroindole. The corresponding mechanism is discussed. These results indicate that 2-(pyridine-2-yl)aniline can serve as a directing group.
- Zhao, Hong-Yi,Wang, Hui-Yan,Mao, Shuai,Xin, Minhang,Zhang, Hao,Zhang, San-Qi
-
p. 6622 - 6631
(2017/08/16)
-
- Control of the Chemoselectivity of Metal N-Aryl Nitrene Reactivity: C-H Bond Amination versus Electrocyclization
-
A mechanism study to identify the elements that control the chemoselectivity of metal-catalyzed N-atom transfer reactions of styryl azides is presented. Our studies show that the proclivity of the metal N-aryl nitrene to participate in sp3-C-H bond amination or electrocyclization reactions can be controlled by either the substrate or the catalyst. Electrocyclization is favored for mono-β-substituted and sterically noncongested styryl azides, whereas sp3-C-H bond amination through an H-atom abstraction-radical recombination mechanism is preferred when a tertiary allylic reaction center is present. Even when a weakened allylic C-H bond is present, our data suggest that the indole is still formed through an electrocyclization instead of a common allyl radical intermediate. The site selectivity of metal N-aryl nitrenes was found to be controlled by the choice of catalyst: Ir(I)-alkene complexes trigger electrocyclization processes while Fe(III) porphyrin complexes catalyze sp3-C-H bond amination in substrates where Rh2(II) carboxylate catalysts provide both products.
- Kong, Chen,Jana, Navendu,Jones, Crystalann,Driver, Tom G.
-
supporting information
p. 13271 - 13280
(2016/10/22)
-
- Efficient metal-free photochemical borylation of aryl halides under batch and continuous-flow conditions
-
A rapid, chemoselective and metal-free C-B bond-forming reaction of aryl iodides and bromides in aqueous solution at low temperatures was discovered. This reaction is amenable to batch and continuous-flow conditions and shows exceptional functional group tolerance and broad substrate scope regarding both the aryl halide and the borylating reagent. Initial mechanistic experiments indicated a photolytically generated aryl radical as the key intermediate.
- Chen, Kai,Zhang, Shuai,He, Pei,Li, Pengfei
-
p. 3676 - 3680
(2016/06/09)
-
- MULTICYCLIC COMPOUND INCLUDING NITROGEN AND ORGANIC LIGHT EMITTING DEVICE USING THE SAME
-
The present invention relates to a polycyclic compound containing nitrogen and an organic light-emitting device comprising the same. The compound is represented by chemical formula 1. The compound of the present invention can be used as an organic matter layer material of the organic light-emitting device.COPYRIGHT KIPO 2016
- -
-
Paragraph 0217-0220
(2016/10/08)
-
- Rh2(II)-catalyzed ester migration to afford 3 H-indoles from trisubstituted styryl azides
-
Rh2(II)-Complexes trigger the formation of 3H-indoles from ortho-alkenyl substituted aryl azides. This reaction occurs through a 4π-electron-5-atom electrocyclization of the rhodium N-aryl nitrene followed by a [1,2]-migration to afford only 3H-indoles. The selectivity of the migration is dependent on the identity of the β-styryl substituent.
- Kong, Chen,Driver, Tom G.
-
supporting information
p. 802 - 805
(2015/04/27)
-
- The method for producing the phenyl boronic acid ester
-
PROBLEM TO BE SOLVED: To provide a method for producing phenylboronic acid esters in good yield from diborons and aryl halides by using a nickel catalyst and a base. SOLUTION: In the method for producing phenylboronic acid esters represented by general formula (3), wherein A is an ethylene group or the like which may be substituted by a methyl group, R1is a fluorine atom or the like, and m is an integer of 0-5; diborons and a chlorobenzene derivative are reacted with each other by using a trimethylphosphine coordinated nickel catalyst and alkoxides. COPYRIGHT: (C)2013,JPOandINPIT
- -
-
Paragraph 0129; 0130
(2018/09/26)
-
- Metal-free C-H amination for indole synthesis
-
An effective metal-free C-H amination of N-Ts-2-alkenylanilines by using DDQ as an oxidant has been developed to afford a diverse range of substituted indoles. This protocol is operationally simple and robust, obviates the need of expensive transition-metal catalysts, and offers a broad substrate scope. A mechanism involving a radical cation generated by SET and a migratorial process via a phenonium ion intermediate is proposed.
- Jang, Young Ho,Youn, So Won
-
supporting information
p. 3720 - 3723
(2014/08/05)
-
- Development of a Suzuki cross-coupling reaction between 2-azidoarylboronic pinacolate esters and vinyl triflates to enable the synthesis of [2,3]-fused indole heterocycles
-
The scope and limitations of a Suzuki reaction between 2-azidoarylboronic acid pinacolate esters and vinyl triflates are reported. This cross-coupling reaction enables the regioselective synthesis of indoles after a subsequent RhII2-catalyzed sp2-C-H bond amination reaction.
- Jana, Navendu,Nguyen, Quyen,Driver, Tom G.
-
p. 2781 - 2791
(2014/04/17)
-
- Efficient synthesis of 3 H-indoles enabled by the lead-mediated α-arylation of β-ketoesters or γ-lactams using aryl azides
-
The development of a lead-mediated α-arylation reaction between aryl azides and β-ketoesters or γ-lactams that facilitates the formation of 3H-indoles is disclosed. Twenty-five examples are included which demonstrate the generality of this reaction to access aryl azides bearing tetrasubstituted o-alkyl substituents. When paired with a Staudinger reduction, this reaction streamlines the synthesis of functionalized 3H-indoles.
- Zhou, Fei,Driver, Tom G.
-
supporting information
p. 2916 - 2919
(2014/06/23)
-
- Process for the preparation of aminoaryl- and aminoheteroaryl boronic acids and esters
-
The present invention relates to a process for the preparation of aminoaryl- and aminoheteroaryl boronic acids and esters of formula (I) in high yields The claimed process uses diarylketal formula (V) to generate an arylbromid of formula (III) in which the amino-group is protected as bisarylmethylidenimino-group:
- -
-
Paragraph 0054; 0056; 0058
(2014/11/27)
-
- PROCESS FOR THE PREPARATION OF AMINOARYL- AND AMINOHETEROARYL BORONIC ACIDS AND ESTERS
-
The present invention relates to a process for the preparation of aminoaryl- and aminoheteroaryl boronic acids and esters thereof of formula (I) in high yield. The claimed process uses diarylketal formula (V) to generate an arylbromide of formula (III) in which the amino-group is protected as bisarylmethylidenimino-group, which is then transformed into a formula (I) compound.
- -
-
Page/Page column 16; 17; 18
(2014/12/09)
-
- Rh2(II)-catalyzed selective aminomethylene migration from styryl azides
-
Rh2(II)-Carboxylate complexes were discovered to promote the selective migration of aminomethylenes in β,β-disubstituted styryl azides to form 2,3-disubstituted indoles. Mechanistic data are also presented that suggest that the migration occurs stepwise before diffusion of the iminium ion.
- Kong, Chen,Jana, Navendu,Driver, Tom G.
-
supporting information
p. 824 - 827
(2013/03/29)
-
- A traceless directing group for C - H borylation
-
Not a trace: Borylation of the nitrogen in nitrogen heterocycles or anilines provides a traceless directing group for subsequent catalytic C - H borylation. Selectivities that previously required Boc protection can be achieved; furthermore, the NBpin directing group can be installed and removed in situ, and product yields are substantially higher. Boc=tert-butoxycarbonyl, pin=pinacolato. Copyright
- Preshlock, Sean M.,Plattner, Donald L.,Maligres, Peter E.,Krska, Shane W.,Maleczka Jr., Robert E.,Smith III, Milton R.
-
supporting information
p. 12915 - 12919
(2014/01/06)
-
- Cesium carbonate mediated borylation of aryl iodides with diboron in methanol
-
Herein we describe the unexpected borylation of aryl iodides promoted by a Cs2CO3 and MeOH system. This formal nucleophilic boryl substitution could be applied to a wide range of functionalized aryl iodide compounds. The preliminary results indicate that this process is neither copper catalyzed nor radical mediated. Copyright
- Zhang, Jieming,Wu, Hai-Hong,Zhang, Junliang
-
supporting information
p. 6263 - 6266
(2013/10/21)
-
- KINASE MODULATING COMPOUNDS, COMPOSITIONS CONTAINING THE SAME AND USE THEREOF
-
The invention provides a compound represented by formula (I) which may modulate a kinase, and a pharmaceutical composition thereof, as well as the method for preventing or treating a protein kinase mediated disease or condition.
- -
-
Page/Page column 54; 55
(2013/06/05)
-
- New synthetic approach to paullones and characterization of their SIRT1 inhibitory activity
-
A series of 7,12-dihydroindolo[3,2-d][1]benzazepine-6(5H)-ones (paullones) substituted at C9/C10 (Br) and C2 (Me, CF3, CO2Me) have been synthesized by a one-pot Suzuki-Miyaura cross-coupling of an o-aminoarylboronic acid and methyl 2-iodoindoleacetate followed by intramolecular amide formation. Other approaches to the paullone scaffold based on Pd-catalyzed C-H activation were unsuccessful. In vitro enzymatic assay with recombinant human SIRT-1 indicated a strong inhibitory profile for the series, in particular the analogue with a methoxycarbonyl group at C2 and a bromine at C9. These compounds are, in general, inducers of granulocyte differentiation of the U937 acute leukemia cell line and cause a marked increase in pre-G1 of the cell cycle.
- Soto, Sara,Vaz, Esther,Dell'Aversana, Carmela,Alvarez, Rosana,Altucci, Lucia,De Lera, Angel R.
-
scheme or table
p. 2101 - 2112
(2012/04/23)
-
- RhII2-catalyzed synthesis of α-, β-, or δ-carbolines from aryl azides
-
Approaching all isomers: A range of α-, β- and δ-carbolinium ions are readily available from ortho-substituted aryl azides using a rhodium(II) carboxylate catalyst (see scheme). The carbolinium ions are readily reduced to afford tryptolines or deprotonated to access pyridoindoles. This [RhII2]-catalyzed C-H bond amination was used in the synthesis of (±)-horsfiline and neocryptolepine. esp=α,α,α',α'- tetramethyl-1,3-benzenedipropionate. Copyright
- Pumphrey, Ashley L.,Dong, Huijun,Driver, Tom G.
-
supporting information; experimental part
p. 5920 - 5923
(2012/08/07)
-
- Enantioselective halocyclization using reagents tailored for chiral anion phase-transfer catalysis
-
A chiral anion phase-transfer system for enantioselective halogenation is described. Highly insoluble, ionic reagents were developed as electrophilic bromine and iodine sources, and application of this system to o-anilidostyrenes afforded halogenated 4H-3,1-benzoxazines with excellent yield and enantioselectivity.
- Wang, Yi-Ming,Wu, Jeffrey,Hoong, Christina,Rauniyar, Vivek,Toste, F. Dean
-
supporting information; experimental part
p. 12928 - 12931
(2012/10/08)
-
- Rhodium-catalyzed synthesis of 2,3-disubstituted indoles from β,β-Disubstituted stryryl azides
-
Rings la carte: Rhodium carboxylate complexes catalyze selective cascade reactions to produce a range 2,3-disubstituted indoles from β,β- disubstituted stryryl azides. The selective migration of aryl groups appears to originate from a putative phenonium ion reactive intermediate (see scheme).
- Sun, Ke,Liu, Sheng,Bec, Patryk M.,Driver, Tom G.
-
supporting information; experimental part
p. 1702 - 1706
(2011/04/24)
-
- NiCl2(PMe3)2-catalyzed borylation of aryl chlorides
-
The cross-coupling of aryl chlorides and bis(pinacolato)diboron was achieved using NiCl2(PMe3)2 catalyst in the presence of metal 2,2,2-trifluoroethoxide. The catalyst smoothly provided the desired products regardless of a variety of functional groups and substituted positions.
- Yamamoto, Tetsuya,Morita, Tomoyuki,Takagi, Jun,Yamakawa, Tetsu
-
supporting information; experimental part
p. 5766 - 5769
(2012/01/06)
-
- An improved procedure for the synthesis of arylboronates by palladium-catalyzed coupling reaction of aryl halides and bis(pinacolato)diboron in polyethylene glycol
-
A new protocol has been developed for the synthesis of arylboronates by a coupling reaction of aryl halides and bis(pinacolato)diboron using bis(triphenylphosphine)palladium dichloride/sodium acetate/polyethylene glycol 600 [Pd(PPh3)2Cl2/NaOAc/PEG 600] as an efficient catalytic system. Copyright
- Lu, Jie,Guan, Zhong-Zhi,Gao, Jian-Wu,Zhang, Zhan-Hui
-
experimental part
p. 537 - 541
(2012/04/04)
-
- Cyclopalladated ferrocenylimine as efficient catalyst for the syntheses of arylboronate esters
-
The cyclopalladated ferrocenylimine I and its phosphine adducts IIa-f were prepared and evaluated in the borylation of aryl halides. The tricyclohexylphosphine adduct IIb exhibited highly catalytic activity for the coupling of aryl and heteroaryl bromides containing various functional groups with low catalyst loading (2 mol%). Aryl and heteroaryl chlorides were smoothly converted into the corresponding boronates in the presence of the monophosphinobiaryl ligand (XPhos) adduct IIf. It was proposed that palladacycle was only a reservoir of the catalytically active species from the investigation on the reaction mechanism.
- Wang, Lianhui,Li, Jingya,Cui, Xiuling,Wu, Yusheng,Zhu, Zhiwu,Wu, Yangjie
-
experimental part
p. 2002 - 2010
(2010/10/19)
-
- PXPd-catalyzed borylation of aniline derivatives
-
Addition of pinacolborane (HBO2C2Me4) to 2-iodoaniline can be catalyzed using a number of palladium complexes, including [(t-Bu)2PCl]2PdCl2 (PXPd), to give the corresponding boronate ester 2-H2NC6H4(BO2C2Me4) in excellent yields. The PXPd system could also be used in the catalyzed borylation of substituted anilines to give the corresponding aminoboronate esters in moderate to high yields.
- Wheaton, Susan L.,Kabir, S.M. Humanayun,Zhang, Haiwen,Vogels, Christopher M.,Decken, Andreas,Westcott, Stephen A.
-
experimental part
p. 725 - 731
(2011/11/04)
-
- Catalytic C-CN activation and asymmetric cyanoamidation of alkenes: Total syntheses of (+)-horsfiline, (-)-coerulescine, and (-)-esermethole
-
The detailed study of Pd-catalyzed asymmetric cyanoamidation is reported. Excellent enantioselectivities are attributed to a chiral phosphosphoramidite ligand synthesized in one step from the commercially available materials. Cyanoamidation substrates are easy to prepare from the corresponding anilines. The 3,3-disubstituted oxindole products bear all-carbon quaternary stereocenters and contain a nitrile and an amide, which are valuable functional handles for the synthesis of many indole-containing natural products. Cyanoamidation tolerates free N-H groups, as demonstrated by the successful use of cyanoamidation in the syntheses of (+)-horsfiline and (-)-coerulescine.
- Reddy, Venkata Jaganmohan,Douglas, Christopher J.
-
scheme or table
p. 4719 - 4729
(2010/08/06)
-
- Regioselective intramolecular electrophilic substitution reactions involving π-deficient pyridine substrates: a new entry to pyridoquinazolines and benzo[h][1,6]naphthyridines
-
Regioselective intramolecular electrophilic substitution reactions have been described in π-deficient pyridine substrates tethered at C-2 to the aryl amine. The presence and nature of ring activating groups at C-6 led to the involvement of either N-1 or C-3 of the pyridine ring in the cyclization thereby leading to the regioselective synthesis of pyridoquinazolines and naphthyridines in excellent yields.
- Agarwal, Piyush K.,Saifuddin, Mohammad,Kundu, Bijoy
-
experimental part
p. 862 - 870
(2010/03/25)
-
- Water-accelerated cationic π-(7-endo) cyclisation: Application to indole-based peri-annulated polyheterocycles
-
An efficient and versatile method for the synthesis of indolebased polycyclic indolo-benzazepine and its derivatives through water-accelerated cationic π-cyclisation is described. The strategy involves condensation of arylamine moieties linked to C-4 in i
- Saifuddin, Mohammad,Agarwal, Piyush K.,Sharma, Sudhir K.,Mandadapu, Anil K.,Gupta, Sahaj,Harit, Vimal K.,Kundu, Bijoy
-
experimental part
p. 5108 - 5117
(2010/11/03)
-
- Convergent, regiospecific synthesis of quinolines from o- aminophenylboronates
-
(Chemical Equation Presented) A direct convergent two-component synthesis of quinolines from αβ-unsaturated ketones and o-aminophenylboronic acid derivatives is reported. The reaction is regiocomplementary to the traditional Skraup-Doebner-Von Miller synthesis and proceeds under basic rather than strongly acidic conditions. Quinolines substituted in the benzenoid ring can be accessed by using substituted o-aminophenylboronates prepared by direct palladium-catalyzed borylation of the corresponding o-bromoanilines.
- Horn, Joachim,Marsden, Stephen P.,Nelson, Adam,House, David,Weingarten, Gordon G.
-
supporting information; experimental part
p. 4117 - 4120
(2009/05/27)
-
- NON-METALLOCENE ORGANOMETALLIC COMPLEXES AND RELATED METHODS AND SYSTEMS
-
A non-metallocene organometallic complex comprising a tridentate ligand and a metal bonded to a tridentate ligand, wherein two substituted aryl groups in the tridentate ligand are connected to a cyclic group at the ortho position via semi-rigid ring-ring linkages, and selected so to provide the resulting non-metallocene organometallic complex with a CS geometry, a C1 geometry, a C2 geometry or a C2v geometry. Method for performing olefin polymerization with a non-metallocene organometallic complex as a catalyst, related catalytic systems, tridentate ligand and method for providing a non-metallocene organometallic complex.
- -
-
Page/Page column 37-38; Sheet 3
(2008/06/13)
-
- Preparation of Aminoaryl and Aminoheteroaryl Boronic Acids and Derivatives Thereof
-
The invention relates to a method for preparation of aminoaryl- or aminoheteroarylboronic acids and esters and salts thereof in which an optionally substituted aminoaryl or aminoheteroaryl compound is protected at its nitrogen site via condensation with a carbonyl compound, subsequently metalated and converted with a suitable boron compound. Depending on the subsequent work-up and removal of the protective group, the corresponding boronic acid, the anhydride or the boronic acid ester thereof is obtained
- -
-
Page/Page column 6
(2008/12/04)
-
- Discovery of conformationally constrained tetracyclic compounds as potent hepatitis C virus NS5B RNA polymerase inhibitors
-
We report a new series of hepatitis C virus NS5B RNA polymerase inhibitors containing a conformationally constrained tetracyclic scaffold. SAR studies led to the identification of 6,7-dihydro-5H-benzo[5,6][1,4]diazepino[7,1-a]indoles (19 and 20) bearing a basic pendent group with high biochemical and cellular potencies. These compounds displayed a very small shift in cellular potency when the replicon assay was performed in the presence of human serum albumin.
- Ikegashira, Kazutaka,Oka, Takahiro,Hirashima, Shintaro,Noji, Satoru,Yamanaka, Hiroshi,Hara, Yoshinori,Adachi, Tsuyoshi,Tsuruha, Jun-Ichiro,Doi, Satoki,Hase, Yasunori,Noguchi, Toru,Ando, Izuru,Ogura, Naoki,Ikeda, Satoru,Hashimoto, Hiromasa
-
p. 6950 - 6953
(2007/10/03)
-
- Thienopyrrole compound and use thereof as HCV polymerase inhibitor
-
The present invention relates to a thienopyrrole compound represented by the following formula [I] wherein each symbol is as defined in the specification, or a pharmaceutically acceptable a salt thereof, and a hepatitis C virus (HCV) polymerase inhibitor and a therapeutic agent for hepatitis C containing this compound as an active ingredient. The compound of the present invention shows an anti-HCV activity based on the HCV polymerase inhibitory activity, and useful as an agent for the prophylaxis or treatment of hepatitis C.
- -
-
Page/Page column 154
(2008/06/13)
-
- FUSED HETEROTETRACYCLIC COMPOUNDS AND USE TEHREOF AS HCV POLYMERASE INHIBITOR
-
The present invention relates to a tetracyclic fused heterocyclic compound represented by the following formula [I] wherein each symbol is as defined in the specification, or a pharmaceutically acceptable a salt thereof, and a hepatitis C virus (HCV) polymerase inhibitor and a therapeutic agent for hepatitis C containing this compound. The compound of the present invention shows an anti-HCV activity based on the HCV polymerase inhibitory activity, and useful as an agent for the prophylaxis or treatment of hepatitis C.
- -
-
-
