- C(sp2)-C(sp2) Suzuki cross-coupling of arylammonium salts catalyzed by a stable Pd–NHC complex
-
We have developed the Suzuki-Miyaura cross-coupling of aryl ammonium salts via C–N bond activation catalyzed by an easily prepared and bench-stable palladium-N-heterocyclic carbene complex. The reaction proceeded well under mild conditions with phenylboronic acid, pinacol ester or anhydride and provided yields of products up to 97% with good functional group compatibility. The direct arylation of arylamine can be performed by a two-step one-pot process and the protocol can be performed on the gram scale.
- Tang, Huiling,Liu, Mengna,Zhu, Meiqi,Cui, Benqiang,Shi, Yanhui,Cao, Changsheng
-
-
- Cobalt-catalyzed C(sp2)?CN bond activation: Cross-electrophile coupling for biaryl formation and mechanistic insight
-
Herein, we report a cross-electrophile coupling of benzonitrile derivatives and aryl halides with a simple cobalt-based catalytic system under mild conditions to form biaryl compounds. Even though the cobalt catalyst is able to activate the C(sp2)?CN bond alone, the use of the AlMe3 Lewis acid enhances the reactivity of benzonitriles and improves the cross-selectivity with barely any influence on the functional group compatibility. X-ray structure determination of an original low-valent cobalt species combined with catalytic and stoichiometric reactions reveals a catalytically active cobalt(I) species toward the aryl halide partner. On the other hand, experimental insights, including cyclic voltammetry experiments, suggest the involvement of a cobalt complex of a lower oxidation state to activate the benzonitrile derivative. Finally, density functional theory calculations support the proposed mechanistic cycle involving two low-valent cobalt species of different oxidation states to perform the reaction.
- Dorval, Céline,Tricoire, Maxime,Begouin, Jeanne-Marie,Gandon, Vincent,Gosmini, Corinne
-
p. 12819 - 12827
(2020/11/18)
-
- Generation of Organozinc Reagents by Nickel Diazadiene Complex Catalyzed Zinc Insertion into Aryl Sulfonates
-
The generation of arylzinc reagents (ArZnX) by direct insertion of zinc into the C?X bond of ArX electrophiles has typically been restricted to iodides and bromides. The insertions of zinc dust into the C?O bonds of various aryl sulfonates (tosylates, mesylates, triflates, sulfamates), or into the C?X bonds of other moderate electrophiles (X=Cl, SMe) are catalyzed by a simple NiCl2–1,4-diazadiene catalyst system, in which 1,4-diazadiene (DAD) stands for diacetyl diimines, phenanthroline, bipyridine and related ligands. Catalytic zincation in DMF or NMP solution at room temperature now provides arylzinc sulfonates, which undergo typical catalytic cross-coupling or electrophilic substitution reactions.
- Klein, Philippe,Lechner, Vivien Denise,Schimmel, Tanja,Hintermann, Lukas
-
p. 176 - 180
(2019/12/11)
-
- Nickel-Catalyzed Stille Cross Coupling of C-O Electrophiles
-
Aryl sulfamates, tosylates, and mesylates undergo efficient Ni-catalyzed cross coupling with diverse organostannanes in the presence of relatively unhindered alkylphosphine ligands and KF. The coupling is valuable for difficult bond constructions, such as aryl - heteroaryl, aryl - alkenyl, and aryl - alkynyl, using nontriflate phenol derivatives. A combination of experimental and computational studies implicates an unusual mechanism for transmetalation involving an 8-centered cyclic transition state. This reaction is inhibited by chloride sources due to slow transmetalation of organostannanes at a Ni(II) - chloride intermediate. These studies help to explain why prior efforts to achieve Ni-catalyzed Stille coupling of phenol derivatives were unsuccessful.
- Russell, John E. A.,Entz, Emily D.,Joyce, Ian M.,Neufeldt, Sharon R.
-
p. 3304 - 3310
(2019/03/26)
-
- A highly efficient and recyclable NiCl2(dppp)/PEG-400 system for Suzuki-Miyaura reaction of aryl chlorides with arylboronic acids
-
NiCl2(dppp) in PEG-400 is shown to be a highly efficient catalyst for Suzuki-Miyaura coupling of aryl chlorides with arylboronic acids. The reaction could be conducted at 100 °C using K3PO4 as base, yielding a variety of biaryls in good to excellent yields. The isolation of the products was readily performed by extraction with petroleum ether and NiCl2(dppp)/PEG-400 system could be easily recycled and reused up to five times without significant loss of activity. Our system not only avoids the use of easily volatile and toxic dioxane or toluene as a solvent but also solves the basic problem of nickel catalyst reuse.
- Liao, Yang,Yang, Weisen,Wei, Ting,Cai, Mingzhong
-
supporting information
p. 1134 - 1142
(2019/04/10)
-
- An efficient class of bis-NHC salts: Applications in Pd-catalyzed reactions under mild reaction conditions
-
This study describes an efficient class of bis-N-heterocyclic carbene (bis-NHC) salts that can be easily made from commercially available and inexpensive starting materials. The application of these salts to Pd-catalyzed reactions is described. The palladium (Pd) catalyst generated in situ was highly effective under mild reaction conditions.
- Chiu, Chien-Cheng,Chiu, Hui-Tzu,Lee, Dong-Sheng,Lu, Ta-Jung
-
p. 26407 - 26415
(2018/08/04)
-
- Synthesis of 3-Arylbenzofuran-2-ylphosphines via Rhodium-Catalyzed Redox-Neutral C-H Activation and Their Applications in Palladium-Catalyzed Cross-Coupling of Aryl Chlorides
-
A new class of aryl-heteroarylphosphines, 3-arylbenzofuran-2-ylphosphines, was synthesized by [Cp?Rh(III)]-catalyzed redox-neutral cyclization of N-phenoxyacetamides with 1-alkynylphosphine sulfides and oxides followed by reduction. This step-economic reaction proceeds in excellent regioselectivity with a broad substrate scope. The application of the resulting air-stable trivalent-phosphine containing dicyclohexylphosphino moiety in palladium-catalyzed Suzuki-Miyaura coupling and Buchwald-Hartwig amination of aryl chlorides is also described.
- Wang, Huanan,Wang, Baiquan,Li, Bin
-
p. 9560 - 9569
(2017/09/23)
-
- An Indefinitely Air-Stable σ-NiII Precatalyst for Quantitative Cross-Coupling of Unreactive Aryl Halides and Mesylates with Aryl Neopentylglycolboronates
-
Three classes of Ni precatalysts based on π-NiII, π-Ni0 and σ-NiII complexes have been elaborated and employed in different laboratories for the functionalization and cross-coupling of otherwise inert aryl C-O, C-Cl, and C-F electrophiles. Various Ni precatalysts, ligands, boron sources, and reaction conditions that were developed in various research groups, necessitated the selection of the most suitable conditions for desired cross-coupling partners. Here a universal, bench-stable, easily prepared NiIICl(1-naphthyl)(PCy3)2/PCy3 σ-complex, for efficient and quantitative cross-coupling of aryl chlorides, bromides, iodides, mesylates, and fluorides with aryl neopentylglycolboronates is reported. This precatalyst will most probably help to advance the applications of Ni catalysis in organic, supramolecular, and macromolecular synthesis and will provide an easier access to the selection of reaction conditions for various transformations.
- Malineni, Jagadeesh,Jezorek, Ryan L.,Zhang, Na,Percec, Virgil
-
supporting information
p. 2795 - 2807
(2016/08/31)
-
- Air-stable nickel precatalysts for fast and quantitative cross-coupling of aryl sulfamates with aryl neopentylglycolboronates at room temperature
-
A library containing 10 air-stable NiIIX(Aryl)(PCy3)2 complexes as precatalysts (X = Cl, Br, OTs, OMs, aryl = 1-naphthyl, 2-naphthyl; X = Cl, 1-acenaphthenyl, 1-(2-methoxynaphthyl), 9-phenanthrenyl, 9-anthracyl) was synthesized and demonstrated to quantitatively cross-couple 2-methoxyphenyl dimethylsulfamate with methyl 4-(5,5-dimethyl-1,3,2-dioxaborinane-2-yl)benzoate at 23 °C in dry THF in the presence of K3PO4(H2O)3.2 in less than 60 min. Lower or higher amounts of H2O in K3PO4 and as received THF mediate the same transformation in a maximum three times longer reaction time.
- Jezorek, Ryan L.,Zhang, Na,Leowanawat, Pawaret,Bunner, Matthew H.,Gutsche, Nicholas,Pesti, Aleksander K. R.,Olsen, James T.,Percec, Virgil
-
p. 6326 - 6329
(2015/02/19)
-
- An efficient suzuki-miyaura coupling of aryl sulfamates and boronic acids catalyzed by NiCl2(dppp)
-
The Suzuki-Miyaura cross-coupling of aryl sulfamates and boronic acids was investigated by using [1,3-bis(diphenylphosphanyl)propane]nickel(II) chloride {NiCl2(dppp)} as the catalyst. The results showed that NiCl 2(dppp) is a highly active and general catalyst that allows effective Suzuki-Miyaura cross-coupling of aryl sulfamates with a slight excess amount of the boronic acid (1.2 equiv.) in the presence of a low catalyst loading (generally 1.0-1.5 mol-%). The method also displays broad generality not only to various aryl sulfamates, but also to an array of boronic acids. Furthermore, various functional groups are tolerated. These apparent advantages make NiCl2(dppp) a practical and reliable catalyst system for the Suzuki-Miyaura coupling of aryl sulfamates.
- Chen, Guo-Jun,Han, Fu-She
-
supporting information; experimental part
p. 3575 - 3579
(2012/07/27)
-
- Nickel catalyzed cross-coupling of aryl C-O based electrophiles with aryl neopentylglycolboronates
-
The efficiency of mesylates, sulfamates, esters, carbonates, carbamates, and methyl ethers as C-O-based electrophiles attached to the 1- or 2-position of naphthalene and to activated and nonactivated phenyl substrates was compared for the first time in Ni-catalyzed cross-coupling with phenyl neopentylglycolboronates containing electron-rich and electron-deficient substituents in their para-position. These experiments were performed in the presence of four different Ni(II)- and Ni(0)-based catalysts. Ni(II)-based catalysts mediate the cross-coupling of most 2-naphthyl C-O electrophiles with both arylboronic acids and with neopentylglycolboronates when K 3PO4 is used as base. The same catalysts are not efficient when CsF is used as base. However, Ni(0)-based catalysts exhibit selective efficiency, and when reactive, their efficiency is higher than that of Ni(II)-based catalysts in the presence of both K3PO4 and CsF. These results provide both reaction conditions for the cross-coupling, and for the elaboration of orthogonal cross-coupling methodologies of various C-O based electrophiles with aryl neopentylglycolboronates. With the exception of mesylates and sulfamates the efficiency of all other 2-naphthyl C-O electrophiles was lower in cross-coupling with aryl neopentylglycolboronates than with arylboronic acids
- Leowanawat, Pawaret,Zhang, Na,Percec, Virgil
-
p. 1018 - 1025
(2012/03/22)
-
- A highly practical and reliable nickel catalyst for Suzuki-Miyaura coupling of aryl halides
-
We disclose that [1,3-bis(diphenylphosphino)methane]nickel(II) chloride [NiCl2(dppp)] is a highly active, universally applicable, cheap, and stable catalyst for Suzuki-Miyaura cross-coupling reactions of aryl halides with a catalyst loading of lower than 1 mol%, and more notably, in the absence of extra supporting ligands. Under the optimized reaction conditions, a broad range of aryl bromides as well as the notoriously unreactive aryl chlorides, including activated, non-activated, deactivated, and heteroaromatic and sterically hindered substrates can be coupled smoothly with various boronic acids (47 examples, 48-98% yields). In addition, the transformation is tolerant of various functional groups such as ether, ester, ketone, aldehyde, cyano, and unprotected amino and hydroxy groups. Finally, the potential utilization of the methodology was further demonstrated by the gram-scale synthesis of several core structures of commercialized antihypertensive drugs and fungicides. Thus, the combination of high activity, broad applicability, cheapness, and high stability of NiCl2(dppp) presented in this work constitutes one of the few prominent catalysts which allow for practical and reliable construction of biaryls and heterobiaryls with structural diversity from readily available aryl halides and boronic acids. Copyright
- Zhao, Yu-Long,Li, You,Li, Shui-Ming,Zhou, Yi-Guo,Sun, Feng-Yi,Gao, Lian-Xun,Han, Fu-She
-
supporting information; experimental part
p. 1543 - 1550
(2011/08/07)
-
- Nickel-catalyzed cross-coupling of phenols and arylboronic acids through an in situ phenol activation mediated by PyBroP
-
A new method for the Suzuki-Miyaura cross-coupling of phenols and arylboronic acids through in situ phenol activation mediated by PyBroP is presented. The reaction proceeds efficiently by using cost-effective, markedly stable [NiCl2(dppp)] (dppp=1,3-bis(diphenylphosphino)propane) as the catalyst in only 5 mol % loading, as well as in the absence of extra ligands. The method exhibits broad applicability and high efficiency towards a wide range of both phenols and boronic acids, including activated, nonactivated, deactivated, and heteroaromatic coupling partners. In addition, various functional groups, such as ether, amino, cyano, ester, and ketone groups, are compatible with this transformation. Notably, arylboronic acids containing an unprotected NH2 group and 2-heterocyclic boronic acids, which are generally problematic for coupling under conventional conditions, are also viable substrates, although moderate yields were obtained for sterically hindered substrates. Consequently, the in situ cross-coupling methodology coupled with the use of an inexpensive and stable nickel catalyst provides a rapid and efficient pathway for the assembly of biaryls and heterobiaryls with structural diversity from readily available phenol compounds.
- Chen, Guo-Jun,Huang, Jie,Gao, Lian-Xun,Han, Fu-She
-
supporting information; experimental part
p. 4038 - 4042
(2011/05/05)
-
- Highly efficient suzuki-miyaura coupling of aryl tosylates and mesylates catalyzed by stable, cost-effective [1,3-bis(diphenylphosphino)propane] nickel(II) chloride [Ni(dppp)Cl2] with only 1amol% loading
-
We present a highly active, inexpensive, universally applicable, and markedly stable [1,3-bis(diphenylphosphino)propane]nickel(II) chloride [Ni(dppp)Cl2] catalyst that is capable of effecting the Suzuki-Miyaura cross-coupling of the inherently less reactive but readily available aryl tosylates and mesylates with only 1amol% loading and in the absence of extra supporting ligand. Under the optimized reaction conditions, cross-coupling of a wide range of activated, non-activated, and deactivated, as well as sterically hindered and heteroaromatic substrates (36 examples) could proceed efficiently to afford the coupled products in 53-99% yields. Consequently, the results presented in this work provide a significant advance in Suzuki-Miyaura cross-coupling in terms of generality, practicality, and cost which are key concerns in recent research regarding transition metal-catalyzed cross-couplings.
- Gao, Han,Li, You,Zhou, Yi-Guo,Han, Fu-She,Lin, Ying-Jie
-
supporting information; experimental part
p. 309 - 314
(2011/04/18)
-
- Aryl phosphoramides: useful electrophiles for suzuki-miyaura coupling catalyzed by a NiCl2/dppp system (dppp=1,3-bis(diphenylphosphino) propane)
-
Chemical Equation presantation Suzuki-Miyaura coupling: We disclose a new strategy for phenol activation in the first Suzuki-Miyaura coupling of phenol derivatives activated by forming aryl bis(2-oxo-3-oxazolidinyl)phosphines as a highly efficient and broadly applicable methodology for the diverse synthesis of biaryls and heterobiaryls (see scheme). The use of readily available, stable NiCl2/dppp as the catalyst system also provides an important advance.
- Zhao, Yu-Long,Li, You,Li, Yu,Gao, Lian-Xun,Han, Fu-She
-
supporting information; experimental part
p. 4991 - 4994
(2010/08/05)
-
- Remarkably effective phosphanes simply with a PPh2 moiety: Application to Pd-Catalysed cross-coupling reactions for tetra-ortho-substituted biaryl syntheses
-
Chemical equation presented Expanding the horizons of ArPPh2: New applications of triarylphosphane ligands are presented. The Pd-L1 and Pd-L2 complexes offer exceptionally high activity in Suzuki-Miyaura cross-couplings of aryl chlorides. The extremely congested synthesis of tetraortho-substituted biaryl compounds is achieved for the first time by simply using triarylphosphane ligands.
- So, Chau Ming,Chow, Wing Kin,Choy, Pui Ying,Lau, Chak Po,Kwong, Fuk Yee
-
supporting information; experimental part
p. 7996 - 8001
(2010/09/05)
-
- PROCESSES FOR THE PREPARATION OF BIPHENYL COMPOUNDS
-
The invention concerns processes for the synthesis of a compound of the formula: wherein: R1 and R2 are each, independently, C1-C12 alkyl, CO2R3, OR4, R5(OR6), or C6-C18 aiyl; R3 -R6 are each, independently, C1-C12 alkyl or C6-C12 aryl; and n and m are each, independently, O or an integer from 1-5; said process comprising: — contacting a compound of the formula H0-R7-0H with BH3 and a compound of the formula in the presence of a nickel-containing catalyst to produce a first product, where R7 is a C2-C12 hydrocarbon group and X is a halogen, OMs or OTs; — contacting the first product in situ with a compound of the formula: in the presence of a nickel-containing catalyst to produce a compound of formula I, where Z is a halogen.
- -
-
Page/Page column 21; 22; 29; 30; 31
(2010/01/29)
-
- Two-step, one-pot ni-catalyzed neopentylglycolborylation and complementary pd/ni-catalyzed cross-coupling with aryl halides, mesylates, and tosylates
-
(Equation Presented) Two-step, one-pot neopentylglycolborylation of aryl iodides and bromides catalyzed by NiCl2(dppe) and NiCl 2(dppp) is reported. Electron-rich and electron-deficient aryl neopentylglycolboronates were efficiently cross-coupled with aryl iodides, bromides, chlorides, mesylates, and tosylates by exploiting complementary Pd/Ni and Ni/Ni catalysis. The borylation route was further extended to a three-step, one-pot synthesis of biaryls via in situ Ni-catalyzed borylation and Pd-mediated cross-coupling.
- Wilson, Daniela A.,Wilson, Christopher J.,Rosen, Brad M.,Percec, Virgil
-
supporting information; scheme or table
p. 4879 - 4882
(2009/05/31)
-
- Synthesis of substituted naphthalenes via a catalytic ring-expansion rearrangement
-
(Figure Presented) A new methodology for the preparation of substituted naphthalenes starting from readily available indenones, organometal reagents, and trimethylsilyldiazomethane via a catalytic rearrangement process is described. Hindered biaryl naphthalenes, including triortho-substituted biaryls, can be accessed through our method. Our results are consistent with a mechanism involving a benzobenzvalene intermediate.
- Glass, Adam C.,Morris, Benjamin B.,Zakharov, Lev N.,Liu, Shih-Yuan
-
supporting information; experimental part
p. 4855 - 4857
(2009/05/31)
-
- Novel tricyclic diazepines tocolytic oxytocin receptor antagonists
-
This invention provides novel tricyclic diazepine compounds as well as methods and pharmaceutical compositions utilizing these compounds for the treatment and/or prevention and/or suppression of disorders which may be remedied or alleviated by oxytocin antagonist activity, including treatment of preterm labor, dysmenorrhea, endometritis, and for suppressing labor prior to caesarean delivery. These compounds are also useful in enhancing fertility rates, enhancing survival rates and synchronizing estrus in farm animals; and may be useful in the prevention and treatment of disfunctions of the oxytocin system in the central nervous system including obsessive compulsive disorder (OCD) and neuropsychiatric disorders.
- -
-
-
- Novel tricyclic pyridyl carboxamides and derivatives thereof tocolytic oxytocin receptor antagonists
-
This invention provides novel substituted tricyclic pyridyl carboxamides which act as oxytocin receptor competitive antagonists, as well as methods of their manufacture, pharmaceutical compositions and methods of their use in treatment, inhibition, suppression or prevention of preterm labor, dysmenorrhea, endometritis, suppression of labor at term prior to caesarean delivery, and to facilitate antinatal transport to a medical facility. These compounds are also useful in enhancing fertility rates, enhancing survival rates and synchronizing estrus in farm animals; and may be useful in the prevention and treatment of disfunctions of the oxytocin system in the central nervous system including obsessive compulsive disorder (OCD) and neuropsychiatric disorders.
- -
-
-
- Novel tricyclic hydroxy carboxamides and derivatives thereof tocolytic oxytocin receptor antagonists
-
This invention provides novel substituted tricyclic carboxamides which act as oxytocin receptor competitive antagonists, as well as methods of their manufacture, pharmaceutical compositions and methods of their use in treatment, inhibition, suppression or prevention of preterm labor, dysmenorrhea and endometritis, suppression of labor at term prior to caesarean delivery, and to facilitate antinatal transport to a medical facility. These compounds are also useful in enhancing fertility rates, enhancing survival rates and synchronizing estrus in farm animals; and may be useful in the prevention and treatment of disfunctions of the oxytocin system in the central nervous system including obsessive compulsive disorder (OCD) and neuropsychiatric disorders.
- -
-
-
- Microwave-Assisted Aqueous Suzuki Cross-Coupling Reactions
-
The poly(ethylene glycol) ester of bromo-, iodo-, and triflate-para-substituted benzoates are smoothly cross-coupled with aryl boronic acids (Suzuki reaction) under "ligandless" palladium acetate catalysis in water. The reaction proceeds without organic cosolvent under conventional thermal conditions (70°C, 2 h) and under microwave irradiation (75 W, 2-4 min). The polymeric support remains stable under both reaction conditions. Whereas conventional thermal conditions induced ester cleavage (up to 45%), this side reaction is suppressed when microwave conditions are employed. Aryl nonaflates give fair yields under these conditions. Non-polymer-bound aryl halides form biaryls in good to excellent yields in water/poly(ethylene glycol) mixtures under microwave irradiation (4 min, 75 W).
- Blettner, Carsten G.,Koenig, Wilfried A.,Stenzel, Wolfgang,Schotten, Theo
-
p. 3885 - 3890
(2007/10/03)
-