cas 54660-04-7, 1-(4-METHOXY-PHENYL)-PYRROLIDINE

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Product selective reaction controlled by the combination of palladium nanoparticles, continuous microwave irradiation, and a co-existing solid; ligand-free Buchwald-Hartwig aminationvs.aryne amination
We have developed a continuous microwave irradiation-assisted Buchwald-Hartwig amination using our original Pd nanoparticle catalyst with a copper plate as a co-existing metal solid. In this methodology, a microwave-controlled product selectivity was achieved between Buchwald-Hartwig amination and aryne amination performed under strongly basic conditions and at a high reaction temperature, because a polar chemical species such as Ar-Pd-halogen might be activated selectively by microwave radiation. Moreover, our catalyst could be used repeatedly over 10 times, and the amount of Pd leaching could be suppressed to a low level.
Akiyama, Toshiki,Arai, Masayoshi,Arisawa, Mitsuhiro,Haneoka, Hitoshi,Harada, Kazuo,Murai, Kenichi,Murakami, Yosuke,Ohki, Yuuta,Ohta, Ryousuke,Sako, Makoto,Sirimangkalakitti, Natchanun,Suzuki, Takeyuki,Takahashi, Naoyuki,Takehara, Tsunayoshi,Yamada, Makito
supporting information
p. 8131 - 8137
(2021/10/29)

peri-Xanthenoxanthene (PXX): a Versatile Organic Photocatalyst in Organic Synthesis
Recent years have witnessed a continuous development of photocatalysts to satisfy the growing demand of photophysical and redox properties in photoredox catalysis, with complex structures or alternative strategies devised to access highly reducing or oxidising systems. We report herein the use of peri-xanthenoxanthene (PXX), a simple and inexpensive dye, as an efficient photocatalyst. Its highly reducing excited state allows activation of a wide range of substrates, thus triggering useful radical reactions. Benchmark transformations such as the addition of organic radicals, generated by photoreduction of organic halides, to radical traps are initially demonstrated. More complex dual catalytic manifolds are also shown to be accessible: the β-arylation of cyclic ketones is successful when using a secondary amine as organocatalyst, while cross-coupling reactions of aryl halides with amines and thiols are obtained when using a Ni co-catalyst. Application to the efficient two-step synthesis of the expensive fluoro-tetrahydro-1H-pyrido[4,3-b]indole, a crucial synthetic intermediate for the investigational drug setipiprant, has been also demonstrated. (Figure presented.).
Pezzetta, Cristofer,Folli, Andrea,Matuszewska, Oliwia,Murphy, Damien,Davidson, Robert W. M.,Bonifazi, Davide
supporting information
p. 4740 - 4753
(2021/04/09)

Enantioselective Synthesis of N-Alkylamines through β-Amino C-H Functionalization Promoted by Cooperative Actions of B(C6F5)3and a Chiral Lewis Acid Co-Catalyst
We disclose a catalytic method for β-C(sp3)-H functionalization of N-alkylamines for the synthesis of enantiomerically enriched β-substituted amines, entities prevalent in pharmaceutical compounds and used to generate different families of chiral catalysts. We demonstrate that a catalyst system comprising of seemingly competitive Lewis acids, B(C6F5)3, and a chiral Mg- or Sc-based complex, promotes the highly enantioselective union of N-alkylamines and α,β-unsaturated compounds. An array of δ-amino carbonyl compounds was synthesized under redox-neutral conditions by enantioselective reaction of a N-alkylamine-derived enamine and an electrophile activated by the chiral Lewis acid co-catalyst. The utility of the approach is highlighted by late-stage β-C-H functionalization of bioactive amines. Investigations in regard to the mechanistic nuances of the catalytic processes are described.
Chang, Yejin,Cao, Min,Chan, Jessica Z.,Zhao, Cunyuan,Wang, Yuankai,Yang, Rose,Wasa, Masayuki
supporting information
p. 2441 - 2455
(2021/02/16)

Dehydrogenation/(3+2) Cycloaddition of Saturated Aza-Heterocycles via Merging Organic Photoredox and Lewis Acid Catalysis
Herein, we report a photoinduced dehydrogenation/(3+2) cycloaddition reaction by merging organic photoredox and Lewis acid catalysis, providing a straightforward and efficient approach for directly installing a benzofuran skeleton on the saturated aza-heterocycles. In this protocol, we also describe a novel organic photocatalyst (t-Bu-DCQ) with the advantages of a wider redox potential, easy synthesis, and a low price. Furthermore, the stepwise activation mechanism of dual C(sp3)-H bonds was demonstrated by a series of experimental and computational studies.
Xiao, Teng-Fei,Zhang, Yi-Fan,Hou, Wen-Tao,Yan, Pen-Ji,Hai, Jun,Xu, Peng-Fei,Xu, Guo-Qiang
supporting information
p. 8942 - 8946
(2021/11/24)

Organic photoredox catalytic α-C(sp3)-H phosphorylation of saturated: Aza -heterocycles
A metal-free C(sp3)-H phosphorylation of saturated aza-heterocycles via the merger of organic photoredox and Br?nsted acid catalyses was established under mild conditions. This protocol provided straightforward and economic access to a variety of valuable α-phosphoryl cyclic amines by using commercially available diarylphosphine oxide reagents. In addition, the D-A fluorescent molecule DCQ was used for the first time as a photocatalyst and exhibited an excellent photoredox catalytic efficiency in this transformation. A series of mechanistic experiments and DFT calculations demonstrated that this transformation underwent a sequential visible light photoredox catalytic oxidation/nucleophilic addition process.
Yi, Ming-Jun,Xiao, Teng-Fei,Li, Wen-Hui,Zhang, Yi-Fan,Yan, Pen-Ji,Zhang, Baoxin,Xu, Peng-Fei,Xu, Guo-Qiang
supporting information
p. 13158 - 13161
(2021/12/16)

Practical direct synthesis of: N -aryl-substituted azacycles from N -alkyl protected arylamines using TiCl4and DBU
A novel transformation of N-alkyl protected arylamines and cyclic ethers into N-aryl substituted azacycles is described. Alkyl groups have been used for the protection of amines in organic syntheses. In this synthesis, N-alkyl protected arylamines were reacted with cyclic ethers in the presence of TiCl4 and DBU, crucial reagents affording five- and six-membered azacycles. In particular, utilization of the novel TiCl4/DBU-mediated reaction allows various N-alkyl protected arylamines such as N-methyl-, N-ethyl-, N-isopropyl, and N-tert-butyl arylamines to be readily converted into N-aryl substituted azacycles in high yields. This practical approach using various N-alkyl arylamines leads to the efficient preparation of azacycles.
Kang, Soosung,Kim, Hee-Kwon,La, Minh Thanh,Tran, Van Hieu
p. 5008 - 5016
(2020/07/30)

Visible Light-Mediated (Hetero)aryl Amination Using Ni(II) Salts and Photoredox Catalysis in Flow: A Synthesis of Tetracaine
We report a visible light-mediated flow process for C-N cross-coupling of (hetero)aryl halides with a variety of amine coupling partners through the use of a photoredox/nickel dual catalyst system. Compared to the method in batch, this flow process enables a broader substrate scope, including less-activated (hetero)aryl bromides and electron-deficient (hetero)aryl chlorides, and significantly reduced reaction times (10 to 100 min). Furthermore, scale up of the reaction, demonstrated through the synthesis of tetracaine, is easily achieved, delivering the C-N cross-coupled products in consistently high yield of 84% on up to a 10 mmol scale.
Park, Boyoung Y.,Pirnot, Michael T.,Buchwald, Stephen L.
p. 3234 - 3244
(2020/02/04)

Metal-free late-stage C(sp2)-H functionalization of: N -aryl amines with various sodium salts
Metal-free consecutive C(sp2)-X (X = Cl, Br, S, N) bond formations of N-aryl amines (cyclic, fused, carbamate, and aminium radicals) were achieved under mild conditions using [bis(trifluoroacetoxy)iodo]benzene (PIFA) and simple nonharmful sodium salts. This direct and selective C(sp2)-H functionalization showed excellent functional group compatibility, cost effectiveness, and late-stage applicability for the synthesis of biologically active natural products. Two mechanisms were proposed to explain the ortho- or para-preference, as well as the accelerating effect of CH3NO2
Mudithanapelli, Chandrashekar,Kim, Mi-Hyun
p. 450 - 464
(2020/02/03)

Dialkylterphenyl Phosphine-Based Palladium Precatalysts for Efficient Aryl Amination of N-Nucleophiles
A series of 2-aminobiphenyl palladacycles supported by dialkylterphenyl phosphines, PR2Ar′ (R=Me, Et, iPr, Cyp (cyclopentyl), Ar′=ArDipp2, ArXyl2f, Dipp (2,6-C6H3-(2,6-C6H3-(CHMe2)2)2), Xyl=xylyl) have been prepared and structurally characterized. Neutral palladacycles were obtained with less bulky terphenyl phosphines (i.e., Me and Et substituents) whereas the largest phosphines provided cationic palladacycles in which the phosphines adopted a bidentate hemilabile k1-P,η1-Carene coordination mode. The influence of the ligand structure on the catalytic performance of these Pd precatalysts was evaluated in aryl amination reactions. Cationic complexes bearing the phosphines PiPr2ArXyl2 and PCyp2ArXyl2 were the most active of the series. These precatalysts have demonstrated a high versatility and efficiency in the coupling of a variety of nitrogen nucleophiles, including secondary amines, alkyl amines, anilines, and indoles, with electronically deactivated and ortho-substituted aryl chlorides at low catalyst loadings (0.25–0.75 mol % Pd) and without excess ligand.
Rama, Raquel J.,Maya, Celia,Nicasio, M. Carmen
supporting information
p. 1064 - 1073
(2020/01/25)

CuI/2-Aminopyridine 1-Oxide Catalyzed Amination of Aryl Chlorides with Aliphatic Amines
A class of 2-aminopyridine 1-oxides are discovered to be effective ligands for the Cu-catalyzed amination of less reactive (hetero)aryl chlorides. A wide range of functionalized (hetero)aryl chlorides reacted with various aliphatic amines to afford the desired products in good to excellent yields under the catalyst of CuI/2-aminopyridine 1-oxides. Furthermore, the catalyst system worked well for the coupling of cyclic secondary amines and N-methyl benzylamine with (hetero)aryl chlorides.
Chen, Xiahong,He, Yongqiang,Liang, Yun,Liu, Wenjie,Wang, Deping,Xia, Xiaohong,Xu, Jiamin,Xu, Zhifeng,Zhang, Fuxing,Zhang, Xin
supporting information
p. 7486 - 7490
(2020/10/12)

Tropane alkaloid compounds and method of manufacturing using sequential oxidation reactions
The present invention relates to a tropane alkaloid compound sequentially using an oxidative Mannich ring reaction and a method for producing the same. The present invention provides a tropane alkaloid compound having a structure of chemical formula 1 in
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Paragraph 0098; 0116-0120

(2020/06/16)

Facile synthesis of hydrochar supported copper nanocatalyst for Ullmann C–N coupling reaction in water
The exploration of inexpensive and stable heterogeneous catalysts and application of green solvents for Ullmann C–N coupling reaction remain challenging. We present a facile fabrication of copper nanoparticles on hydrochar as prepared from natural, inexpensive and renewable chitosan together with in-situ reduction of copper salt in a one-pot hydrothermal carbonization process. The copper nanoparticles were uniformly dispersed on hydrochar by choosing block copolymer F127 as surfactant. Moreover, maleic acid was introduced to improve the hydrophilicity of hydrochar. The most active copper nanocomposite catalyst, that is, Cu/HCS-MA-F127, exhibited excellent catalytic activity for Ullmann C–N coupling reaction in water. The nature of the Cu/HCS-MA-F127 was characterized by FTIR spectroscopy, TG, XRD, SEM and XPS. Moderate to excellent yields of aimed products were gained by using this catalytic strategy. Moreover, the Cu/HCS-MA-F127 catalyst can be reused by simple centrifugal recovery with a stable performance.
Ge, Xin,Ge, Meng,Chen, Xinzhi,Qian, Chao,Liu, Xuemin,Zhou, Shaodong
(2019/12/24)

Organocatalytic Cascade β-Functionalization/Aromatization of Pyrrolidines via Double Hydride Transfer
An unprecedented cascade β-functionalization/aromatization reaction of N-arylpyrrolidines was established. A series of β-substituted arylpyrroles embedded with trifluoromethyl groups are provided directly from N-arylpyrrolidines. The deuterium-labeling experiments indicate that sequential double hydride transfer processes serve as the key steps in this transformation.
An, Xiao-De,Li, Xian-Jiang,Liu, Qing,Shao, Chang-Lun,Xiao, Jian,Yang, Shuo,Zhou, Lan
supporting information

(2020/02/15)

Utilization of Cyclic Amides as Masked Aldehyde Equivalents in Reductive Amination Reactions
An operationally simple protocol has been discovered that couples primary or secondary amines with N-aryl-substituted lactams to deliver differentiated diamines in moderate to high yields. The process allows for the partial reduction of a lactam in the presence of Cp2ZrHCl (Schwartz's reagent), followed by a reductive amination between the resulting hemiaminal and primary or secondary amine. These reactions can be telescoped in a one-pot fashion to significantly simplify the operation. The scope of amines and substituted lactams of various ring sizes was demonstrated through the formation of a range of differentiated diamine products. Furthermore, this methodology was expanded to include N-aryl pyrrolidinone substrates with an enantiopure ester group at the 5-position, and α-amino piperidinones were prepared with complete retention of stereochemical information. The development of this chemistry has enabled the consideration of lactams as useful synthons.
Prince, Robin J.,Gao, Fang,Pazienza, Jessica E.,Marx, Isaac E.,Schulz, Jurgen,Hopkins, Brian T.
p. 7936 - 7949
(2019/06/27)

PIFA-Promoted, Solvent-Controlled Selective Functionalization of C(sp2)-H or C(sp3)-H: Nitration via C-N Bond Cleavage of CH3NO2, Cyanation, or Oxygenation in Water
A novel nitration (via C(sp3)-N breaking/C(sp2)-N formation with CH3NO2) mediated by [bis(trifluoroacetoxy)iodo]benzene (PIFA) is described. The NO2 transfer from CH3NO2 to the aromatic group of the substrate is possible with careful selection of the solvent, NaX, and oxidant. In addition, the solvent-controlled C(sp2)-H functionalization can shift to an α-C(sp3)-H functionalization (cyanation or oxygenation) of the α-C(sp3)-H of cyclic amines.
Mudithanapelli, Chandrashekar,Dhorma, Lama Prema,Kim, Mi-Hyun
supporting information

(2019/05/07)

Palladate Precatalysts for the Formation of C-N and C-C Bonds
A series of imidazolium-based palladate precatalysts has been synthesized and the catalytic activity of these air- and moisture-stable complexes evaluated as a function of the nature of the imidazolium counterion. These precatalysts can be converted under
Zinser, Caroline M.,Warren, Katie G.,Nahra, Fady,Al-Majid, Abdullah,Barakat, Assem,Islam, Mohammad Shahidul,Nolan, Steven P.,Cazin, Catherine S. J.
p. 2812 - 2817
(2019/08/12)

A Newly Designed Carbohydrate-Derived Alkylamine Promotes Ullmann Type C-N Coupling Catalyzed by Copper in Water
A green and biodegradable carbohydrate-derived alkylamine was designed and employed as ligand for Ullmann type C-N coupling catalyzed by copper in water. The coupling of aryl iodide and N-nucleophiles were examined and moderate to excellent yields were obtained. In addition, the in-water coupling strategy was expanded successfully to the reaction of indoles with 4-iodoanisole. By measuring the solubility, it is speculated that carbohydrate-derived alkylamine plays the role of chelating copper and promoting the dissolution of 4-iodoanisole in water. Remarkably, this methodology was environmentally friendly and economical because of the use of aqueous media in place of organic solvents.
Zhou, Guoquan,Chen, Wen,Zhang, Shihui,Liu, Xuemin,Yang, Zehui,Ge, Xin,Fan, Hua-Jun
supporting information
p. 193 - 198
(2019/01/14)

A designed bi-functional sugar-based surfactant: Micellar catalysis for C-X coupling reaction in water
A bi-functional sugar-based surfactant ALA14 was designed as the ligand and micelle constructor and demonstrated to promote the copper-catalyzed C-X coupling reaction in water. The nature of this micelle, formed by sugar-based surfactants, was investigated with CMC, DLS, and TEM, by which encapsulation and aggregation of the substrates in micelles were verified. Additionally, it was addressed by 1H-NMR analysis that the enrichment position of the substrates is in the lipophilic alkyl chain. Finally, moderate to excellent yields of the aimed products were obtained in this work. This remarkably simple strategy expanded the scope of C-X coupling reaction in water; most notably, both water and ALA14 can be recycled and reused.
Ge, Xin,Zhang, Shihui,Chen, Xinzhi,Liu, Xuemin,Qian, Chao
supporting information
p. 2771 - 2776
(2019/06/13)

A Highly Selective Palladium-Catalyzed Aerobic Oxidative Aniline-Aniline Cross-Coupling Reaction
The first catalytic oxidative aniline-aniline cross-coupling reaction using oxygen as the terminal oxidant is reported. Anilines possessing a pyrrolidino group can be preferentially oxidized under mild aerobic conditions and reacted with other anilines to afford a variety of nonsymmetrical 2-aminobiphenyls with high selectivities. A heterogeneous palladium catalyst is used for the dehydrogenative cross-coupling of anilines with structurally diverse arenes. This reaction does not require stoichiometric oxidants and is an economical and environmentally friendly method.
Matsumoto, Kenji,Takeda, Satoshi,Hirokane, Tsukasa,Yoshida, Masahiro
supporting information
p. 7279 - 7283
(2019/09/30)

Visible-Light-Mediated C(sp3)–H Thiocarbonylation for Thiolactam Preparation with Potassium Sulfide
We report herein a protocol for thiolactam preparation with potassium sulfide via visible-light-mediated C(sp3)–H thiocarbonylation, in which polysulfide dianions and radical anions generated from potassium sulfide were the key active species. A variety of thiolactams were straightforward established under mild conditions. Moreover, it was successfully applied to structural modification of tetrahydroberberine.
Tan, Wei,Wang, Cuihong,Jiang, Xuefeng
supporting information
p. 1234 - 1238
(2019/11/21)

COMPOSITIONS AND METHODS OF PROMOTING ORGANIC PHOTOCATALYSIS
The invention provides novel compounds and methods that are useful in promoting reactions that proceed through an oxidative quenching pathway. In certain embodiments, the reactions comprise atom transfer radical polymerization.
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Paragraph 0067-0068; 0218

(2018/09/12)

An Effective Heterogeneous Copper Catalyst System for C-N Coupling and Its Application in the Preparation of 2-Methyl-4-methoxydiphenylamine (MMDPA)
A ligand-recyclable, environmentally benign heterogeneous catalyst system composed of CuI and polystyrene-supported N (-(4-(aminomethyl)naphthalen-1-yl)- N (-phenyl-1 H -pyrrole-2-carbohydrazide (PSAP) has been established for Ullmann type C-N coupling based on the homogeneous catalyst system N ′, N ′-diphenyl-1 H -pyrrole-2-carbohydrazide/CuI. This heterogeneous catalyst system maintained the catalytic effectiveness of the homogeneous catalyst. A variety of functionalized aryl bromides can be efficiently aminated with aryl amines and aliphatic amines with high selectivity for amines over alcohols. Moreover, a practical application of this catalyst system to promote the reaction of commercially available 4-methoxy-2-methylaniline and bromobenzene in 10 mmol scale, provided 2-methyl-4-methoxydiphenylamine (MMDPA) with 93% yield with the merit of the approach being simple operation for work-up and purification.
Yi, Zhou,Huang, Manna,Wan, Yiqian,Zhu, Xinhai
p. 3911 - 3920
(2018/09/29)

Synergistic Ligand Effect between N-Heterocyclic Carbene (NHC) and Bicyclic Phosphoramidite (Briphos) Ligands in Pd-Catalyzed Amination
A synergistic ligand effect between NHC and phosphorus ligands in Pd-catalyzed Buchwald-Hartwig amination reactions was demonstrated with tunable π-acceptor bicyclic bridgehead phosphoramidite (briphos) ligands. The catalytic activity of NHC-Pd-L (L = phosphorus ligand) precatalysts depends on the electronic properties of L. A NHC-Pd-L catalyst with an N-cyclohexyl-substituted briphos ligand was found to be highly efficient. A series of C-N bond coupling reactions between primary or secondary amines and aryl chlorides were performed with high yields under mild reaction conditions.
Kim, Miji,Shin, Taeil,Lee, Ansoo,Kim, Hyunwoo
supporting information
p. 3253 - 3258
(2018/10/02)

Construction of 8-Azabicyclo[3.2.1]octanes via Sequential DDQ-Mediated Oxidative Mannich Reactions of N-Aryl Pyrrolidines
A concise synthesis of 8-azabicyclo[3.2.1]octanes via sequential oxidative Mannich reactions is described. This approach involves an intermolecular oxidative Mannich coupling reaction between N-aryl pyrrolidines with TMS enol ether and a subsequent intramolecular oxidative Mannich cyclization of the corresponding silyl enol ether. DDQ is used as a key oxidant for both reactions.
Jo, Hanbyeol,Hassan, Ahmed H. E.,Jung, Seung Young,Lee, Jae Kyun,Cho, Yong Seo,Min, Sun-Joon
supporting information
p. 1175 - 1178
(2018/02/23)

Ultrafine hybrid Cu2O-Fe2O3 nanoparticles stabilized by hexaphenylbenzene-based supramolecular assemblies: A photocatalytic system for the Ullmann-Goldberg coupling reaction
Ultrafine hybrid Cu2O-Fe2O3 NPs have been prepared using the supramolecular assemblies of hexaphenylbenzene (HPB) derivative 3 as nanoreactors and stabilizers. The as-prepared hybrid Cu2O-Fe2O3 NPs serve as an efficient and recyclable photocatalytic system for carrying out C-N coupling between aryl halides and various amines (aliphatic, aromatic and N-heterocyclic) at room temperature in mixed aqueous media under visible light irradiation. Amazingly, Cu2O-Fe2O3 NPs also exhibited high efficiency in the reactions involving the synthesis of biologically important N-substituted carbazole derivatives. The work being presented in this article demonstrates the preparation of a 'dip strip' coated with the as-prepared catalytic system and utilization of this paper strip as a recyclable and portable heterocatalytic system for carrying out the Ullmann-Goldberg coupling.
Singh, Gurpreet,Kumar, Manoj,Bhalla, Vandana
p. 5346 - 5357
(2018/12/05)

Efficient Ullmann C-X coupling reaction catalyzed by a recoverable functionalized-chitosan supported copper complex
Three different types of functionalized-CS were prepared and anchored with copper salts for use as the catalyst for the Ullmann C-X coupling reaction. The Schiff-basic chitosan supported copper complex (PCCS@CuI) exhibits the highest catalytic activity. The structure of the catalyst was characterized by FTIR spectroscopy, TG, XRD, SEM, EDS and XPS. This catalyst exhibited high applicability for the C-N and C-S coupling reactions, in which good to excellent yields were obtained. Its easy separation, good reusability and stability were notable.
Liu, Xuemin,Chang, Shuo,Chen, Xinzhi,Ge, Xin,Qian, Chao
supporting information
p. 16013 - 16020
(2018/10/04)

"on Water" Promoted Ullmann-Type C-N Bond-Forming Reactions: Application to Carbazole Alkaloids by Selective N-Arylation of Aminophenols
The Ullmann-type cross coupling of a variety of aromatic, aliphatic amines with aryl halides is reported using a CuI-based catalytic system in combination with an easily accessible prolinamide ligand in aqueous media. The method is mild and tolerant to air, moisture, and a wide range of functional groups, providing a novel way to access a variety of aminated products. Secondary amines like heteroaromatic amines and nucleobases have also been used, affording the corresponding coupling products in good to excellent yields. Moreover, this method has been employed for chemoselective C-N arylation of aminophenols and further utilized for the synthesis of carbazole natural products, avoiding the protection and deprotection steps.
Chakraborti, Gargi,Paladhi, Sushovan,Mandal, Tirtha,Dash, Jyotirmayee
p. 7347 - 7359
(2018/07/29)

Dual C(sp3)?H Bond Functionalization of N-Heterocycles through Sequential Visible-Light Photocatalyzed Dehydrogenation/[2+2] Cycloaddition Reactions
Herein we describe a mild method for the dual C(sp3)?H bond functionalization of saturated nitrogen-containing heterocycles through a sequential visible-light photocatalyzed dehydrogenation/[2+2] cycloaddition procedure. As a complementary approach to the well-established use of iminium ion and α-amino radical intermediates, the elusive cyclic enamine intermediates were effectively generated by photoredox catalysis under mild conditions and efficiently captured by acetylene esters to form a wide array of bicyclic amino acid derivatives, thus enabling the simultaneous functionalization of two vicinal C(sp3)?H bonds.
Xu, Guo-Qiang,Xu, Ji-Tao,Feng, Zhi-Tao,Liang, Hui,Wang, Zhu-Yin,Qin, Yong,Xu, Peng-Fei
supporting information
p. 5110 - 5114
(2018/03/27)

Metal-free protocol for the synthesis of N-arylpyrrolidines catalyzed by hydrogen iodine
A metal-free and efficient approach to N-arylpyrrolidines from arylamines and cyclic ethers catalyzed by hydrogen iodine is described. In this protocol, no additive is added and a wide range of N-arylpyrrolidines are synthesized with up to 99% yield. Reaction mechanism involving iodine radical is proposed.
Hou, Tingting,Zhang, Chaofeng,Wang, Yehong,Liu, Zhenting,Zhang, Zhixin,Wang, Feng
p. 56 - 59
(2017/03/09)

Strongly Reducing, Visible-Light Organic Photoredox Catalysts as Sustainable Alternatives to Precious Metals
Photoredox catalysis is a versatile approach for the construction of challenging covalent bonds under mild reaction conditions, commonly using photoredox catalysts (PCs) derived from precious metals. As such, there is need to develop organic analogues as sustainable replacements. Although several organic PCs have been introduced, there remains a lack of strongly reducing, visible-light organic PCs. Herein, we establish the critical photophysical and electrochemical characteristics of both a dihydrophenazine and a phenoxazine system that enables their success as strongly reducing, visible-light PCs for trifluoromethylation reactions and dual photoredox/nickel-catalyzed C?N and C?S cross-coupling reactions, both of which have been historically exclusive to precious metal PCs.
Du, Ya,Pearson, Ryan M.,Lim, Chern-Hooi,Sartor, Steven M.,Ryan, Matthew D.,Yang, Haishen,Damrauer, Niels H.,Miyake, Garret M.
supporting information
p. 10962 - 10968
(2017/08/22)

Room-Temperature CuI-Catalyzed Amination of Aryl Iodides and Aryl Bromides
A general and effective CuI/N′,N′-diaryl-1H-pyrrole-2-carbohydrazide catalyst system was developed for the amination of aryl iodides and bromides at room temperature with good chemoselectivity between -OH and -NH2 groups. Only 5 mol % of CuI and ligands was needed in this protocol to effect the amination of various aryl bromides and aryl iodides with a wide range of aliphatic and aryl amines (1.3 equiv).
Ding, Xiaomei,Huang, Manna,Yi, Zhou,Du, Dongchen,Zhu, Xinhai,Wan, Yiqian
p. 5416 - 5423
(2017/05/25)

Room-Temperature Practical Copper-Catalyzed Amination of Aryl Iodides
An efficient and highly practical procedure is reported for the Ullmann-Goldberg-type copper-catalyzed amination of aryl iodides. By using a combination of copper iodide and proline in the presence of an excess of an amine, a wide range of aryl iodides can be readily aminated at room temperature. The reaction proceeds well regardless of the electronic properties of the starting aryl iodide and the amination products can be obtained without the need for purification by column chromatography in most cases. Owing to its efficiency and the mildness of the reaction conditions, this amination could also be extended to the amination of complex aryl iodides at room temperature.
Deldaele, Christopher,Evano, Gwilherm
p. 1319 - 1328
(2016/04/20)

Combined experimental/theoretical study of D-glucosamine promoted Ullmann-type C-N coupling catalyzed by copper(I): Does amino really count?
Ullmann type C-N coupling reaction catalyzed by copper(I) with D-glucosamine derivatives as promoters was studied by means of combined experimental/theoretical investigation. The catalytic role of D-glucosamine was addressed. In contrast with previous speculations, the amino group may not count in the catalytic cycle in which the oxidative addition/reductive elimination mechanism works. Experimental results are in good agreement with theoretical findings. Extensive work indicates the wide applicability of the C-N coupling strategy exploited in this work.
Ge, Xin,Chen, Xinzhi,Qian, Chao,Zhou, Shaodong
p. 29638 - 29645
(2018/06/04)

Efficient Ullmann C-N coupling catalyzed by a recoverable oligose-supported copper complex
The natural compound β-cyclodextrin supported copper complex (CuIβ-CD) was prepared and employed as catalyst for an Ullmann-type C-N coupling reaction of N-nucleophiles and aryl halides under mild conditions. Reactions with different substrates were examined, and moderate to excellent yields were obtained. In addition to the high efficiency, the reaction system is also noticeable due to the excellent recoverability and reusability of the catalyst.
Ge, Xin,Chen, Xinzhi,Qian, Chao,Zhou, Shaodong
p. 58898 - 58906
(2016/07/06)

Direct Acylation of C(sp3)-H Bonds Enabled by Nickel and Photoredox Catalysis
Using nickel and photoredox catalysis, the direct functionalization of C(sp3)-H bonds of N-aryl amines by acyl electrophiles is described. The method affords a diverse range of α-amino ketones at room temperature and is amenable to late-stage coupling of complex and biologically relevant groups. C(sp3)-H activation occurs by photoredox-mediated oxidation to generate α-amino radicals which are intercepted by nickel in catalytic C(sp3)-C coupling. The merger of these two modes of catalysis leverages nickel's unique properties in alkyl cross-coupling while avoiding limitations commonly associated with transition-metal-mediated C(sp3)-H activation, including requirements for chelating directing groups and high reaction temperatures. Teamwork: The direct functionalization of C(sp3)-H bonds of N-aryl amines by acyl electrophiles is achieved, thus affording a diverse range of α-amino ketones at room temperature. C(sp3)-H activation occurs by photoredox-mediated oxidation to generate α-amino radicals which are intercepted by nickel in catalytic C(sp3)-C coupling.
Joe, Candice L.,Doyle, Abigail G.
supporting information
p. 4040 - 4043
(2016/03/19)

Copper-Catalyzed para-Selective C-H Amination of Electron-Rich Arenes
A one-pot two-step method for para-selective C-H amination of carbocyclic arenes comprises the in situ formation of unsymmetrical diaryl-λ3-iodanes followed by their Cu(I)-catalyzed reaction with a range of N-unprotected amines.
Berzina, Beatrise,Sokolovs, Igors,Suna, Edgars
p. 7008 - 7014
(2015/11/23)

N-(1-Oxy-2-picolyl)oxalamic Acid as an Efficient Ligand for Copper-Catalyzed Amination of Aryl Iodides at Room Temperature
N-(1-Oxy-pyridin-2-ylmethyl)oxalamic acid was identified as efficient ligand for CuI-catalyzed amination of aryl halides at room temperature. In our catalytic system, N-arylation of cyclic secondary amines, primary amines, amino acids, and ammonia proceeded with moderate to excellent yields and high functional group tolerance.
Wang, Yongbin,Ling, Jing,Zhang, Yu,Zhang, Ao,Yao, Qizheng
p. 4153 - 4161
(2015/07/01)

An efficient d-glucosamine-based copper catalyst for C-X couplings and its application in the synthesis of nilotinib intermediate
d-Glucosamine has been studied for C-N and C-S bond formations via cross-coupling reactions of nitrogen and sulfur nucleophiles with both aryl iodides and bromides. Imidazoles, benzimidazole, indole, pyrrolidine and diphenyl disulfide undergo reactions with aryl halides in the presence of 10 mol% d-glucosamine, 10 mol% CuI, and 2 equiv. of Cs2CO3 in DMSO-H2O at moderate temperature to give the corresponding products in good to excellent yields. Substrates bearing halides, free amino groups, trifluoromethyl and heterocycles were well tolerated. The high water solubility of the ligand enables easy catalyst removal. In addition, the application of this catalytic system for the synthesis of nilotinib intermediate was also successfully demonstrated using commercially available substrates. This journal is
Wen, Ming,Shen, Chao,Wang, Linfang,Zhang, Pengfei,Jin, Jianzhong
p. 1522 - 1528
(2015/02/18)

Alkylation of Amines with Alcohols and Amines by a Single Catalyst under Mild Conditions
An efficient catalytic system for the alkylation of amines with either alcohols or amines under mild conditions has been developed, using cyclometallated iridium complexes as catalysts. The method has broad substrate scope, allowing for the synthesis of a diverse range of secondary and tertiary amines with good to excellent yields. By controlling the ratio of substrates, both mono- and bis-alkylated amines can be obtained with high selectivity. In particular, methanol can be used as the alkylating reagent, affording N-methylated products selectively. A strong solvent effect is observed for the reaction.
Zou, Qingzhu,Wang, Chao,Smith, Jen,Xue, Dong,Xiao, Jianliang
supporting information
p. 9656 - 9661
(2015/06/30)

Copper(I) 3-methylsalicylate, an efficient catalyst for N-arylation of heterocycles under moderate reaction conditions
Copper(I) 3-methylsalicylate mediates N-arylation reactions of both aliphatic and aromatic heterocycles under moderate reaction conditions. Both electron rich and electron poor aryl bromides and a diverse set of N-heterocycles were allowed to react and gave N-arylation products in high yields which demonstrated the efficiency and utility of this catalyst.
Farahat, Abdelbasset A.,Boykin, David W.
supporting information
p. 3049 - 3051
(2014/05/20)

Skeleton decoration of NHCs by amino groups and its sequential booster effect on the palladium-catalyzed Buchwald-Hartwig amination
A challenging synthetic modification of PEPPSI-type palladium pre-catalysts consisting of a stepwise incorporation of one and two amino groups onto the NHC skeleton was seen to exert a sequential enhancement of the electronic donor properties. This appears to be positively correlated with the catalytic performances of the corresponding complexes in the Buchwald-Hartwig amination. This is illustrated, for example, by the quantitative amination of 4-chloroanisole by morpholine within 2 h at 25°C with a 2 mol% catalyst/substrate ratio or by a significant reduction of catalytic loading (down to 0.005 mol%) for the coupling of aryl chlorides with anilines (max TON: 19600).
Zhang, Yin,Cesar, Vincent,Storch, Golo,Lugan, Noel,Lavigne, Guy
supporting information
p. 6482 - 6486
(2014/06/24)

Magnetic silica supported copper: A modular approach to aqueous Ullmann-type amination of aryl halides
One-pot synthesis of a magnetic silica supported copper catalyst has been described via in situ generated magnetic silica (Fe3O 4@SiO2); the catalyst can be used for the efficacious amination of aryl halides in aqueous medium under microwave irradiation.
Nasir Baig,Varma, Rajender S.
p. 6568 - 6572
(2014/02/14)

Synthesis of N-arylsubstituted pyrrolidines and piperidines by reaction of anilines with α,ω-diols catalyzed by FeCl3·6H2O in carbon tetrachloride
N-Arylpyrrolidines and N-arylpiperidines were synthesized in 20-88% yields by the reaction of aniline and aniline derivatives with 1,4-butane- and 1,5-pentanediols in the presence of Fecontaining catalysts and carbon tetrachloride. 1,4-Butane- and 1,5-pentanediols are partially chlorinated under the reaction conditions to give chlorohydrins, which subsequently undergo Nheterocyclization with anilines to give N-arylpyrrolidines and N-arylpiperidines.
Khusnutdinov, Ravil I.,Bayguzina, Alfiya R.,Asylbaeva, Rigina S.,Aminov, Rishat I.,Dzhemilev, Usein M.
p. 341 - 350
(2014/12/12)

Photoredox α-vinylation of α-amino acids and N -aryl amines
A new coupling protocol has been developed that allows the union of vinyl sulfones with photoredox-generated α-amino radicals to provide allylic amines of broad diversity. Direct C-H vinylations of N-aryl tertiary amines, as well as decarboxylative vinylations of N-Boc α-amino acids, proceed in high yield and with excellent olefin geometry control. The utility of this new allyl amine forming reaction has been demonstrated via the syntheses of several natural products and a number of established pharmacophores.
Noble, Adam,MacMillan, David W. C.
supporting information
p. 11602 - 11605
(2014/11/08)

Homogeneous catalytic hydrogenation of amides to amines
Hydrogenation of amides in the presence of [Ru(acac)3] (acacH=2,4-pentanedione), triphos [1,1,1-tris- (diphenylphosphinomethyl)ethane] and methanesulfonic acid (MSA) produces secondary and tertiary amines with selectivities as high as 93 % provided that there is at least one aromatic ring on N. The system is also active for the synthesis of primary amines. In an attempt to probe the role of MSA and the mechanism of the reaction, a range of methanesulfonato complexes has been prepared from prepared from [Ru(acac) 3], triphos and MSA, or from reactions of [RuX-(OAc)(triphos)] (X=H or OAc) or [RuH2(CO)(triphos)] with MSA. Crys-tallographically characterised complexes include: [Ru(OAc-κ1O) 2(H2O)-(triphos)], [Ru(OAc-κ2O,O') (CH3SO3-κ1O)(triphos)], [Ru(CH 3SO3-κ1O)2-(H 2O)(triphos)] and [Ru2(μ-CH3SO 3)3-(triphos)2][CH3SO3], whereas other complexes, such as [Ru(OAc-κ1O)(OAc- κ2O,O')(triphos)],[Ru(CH3SO3- κ1O)(CH3SO3-κ2O,O')- (triphos)], H[Ru(CH3SO3-κ1O) 3-(triphos)], [RuH(CH3SO3-κ1O) (CO)-(triphos)] and [RuH(CH3SO3-k2O,O')- (triphos)] have been characterised spectroscopically. The interactions between these various complexes and their relevance to the catalytic reactions are discussed.
Coetzee, Jacorien,Dodds, Deborah L.,Klankermayer, Jürgen,Brosinski, Sandra,Leitner, Walter,Slawin, Alexandra M. Z.,Cole-Hamilton, David J.
supporting information
p. 11039 - 11050
(2013/09/02)

Nickel-catalyzed coupling of fluoroarenes and amines
The combination of bis(cyclooctadiene)nickel [Ni(COD)2] and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene hydrochloride (IPr×HCl) effectively catalyzes coupling of fluoroarenes with amines in the presence of sodium tert-butoxide (t-BuONa). A
Zhu, Feng,Wang, Zhong-Xia
p. 3694 - 3702
(2014/01/06)

Synthesis and structural characterization of palladium(II) thiosemicarbazone complex: Application to the Buchwald-Hartwig amination reaction
A simple route to synthesize mononuclear palladium(II) thiosemicarbazone complex has been described. Elemental analysis, spectral methods and single crystal X-ray diffraction analysis were used to confirm the composition of the complex. The new complex acts as an active homogeneous catalyst for the Buchwald-Hartwig amination reaction of a wide range of aryl and heteroaryl halides (bromides and chlorides), including activating, neutral and deactivating substrates, with various secondary amines under optimized conditions.
Prabhu, Rupesh Narayana,Ramesh, Rengan
p. 1120 - 1124
(2013/03/13)

Development of a general non-noble metal catalyst for the benign amination of alcohols with amines and ammonia
The N-alkylation of amines or ammonia with alcohols is a valuable route for the synthesis of N-alkyl amines. However, as a potentially clean and economic choice for N-alkyl amine synthesis, non-noble metal catalysts with high activity and good selectivity are rarely reported. Normally, they are severely limited due to low activity and poor generality. Herein, a simple NiCuFeOx catalyst was designed and prepared for the N-alkylation of ammonia or amines with alcohol or primary amines. N-alkyl amines with various structures were successfully synthesized in moderate to excellent yields in the absence of organic ligands and bases. Typically, primary amines could be efficiently transformed into secondary amines and N-heterocyclic compounds, and secondary amines could be N-alkylated to synthesize tertiary amines. Note that primary and secondary amines could be produced through a one-pot reaction of ammonia and alcohols. In addition to excellent catalytic performance, the catalyst itself possesses outstanding superiority, that is, it is air and moisture stable. Moreover, the magnetic property of this catalyst makes it easily separable from the reaction mixture and it could be recovered and reused for several runs without obvious deactivation. Copyright
Cui, Xinjiang,Dai, Xingchao,Deng, Youquan,Shi, Feng
supporting information
p. 3665 - 3675
(2013/03/29)

Efficient catalytic aryl amination of bromoarenes using 3-iminophosphine palladium(II) chloride
While pursuing the development of new hydroamination catalysts, a 3-iminophosphine palladium(II) chloride complex [(3IP)PdCl2] was synthesized that has subsequently proven to be an effective precatalyst for the aryl amination of bromoarenes. This (3IP)PdCl2 complex has been utilized in the catalytic aryl amination of both bromobenzene and bromopyridine derivatives, specifically yielding excellent activity in coupling reactions involving bromobenzene, 4-bromotoluene, and 2-bromopyridine. Using a standard set of catalytic conditions, many alkyl and aryl amines have been investigated as coupling partners in the aryl amination of bromoarenes. In general, secondary alkyl amines and ortho-substituted anilines proved to be the best substrates for this reaction, commonly giving quantitative conversion to products, while primary amines and other anilines gave only poor to moderate results. Catalytic screening data, product yields, and full characterization of isolated products are included.
Samblanet, Danielle C.,Schmidt, Joseph A. R.
p. 7 - 18,12
(2012/12/12)

N-heterocyclization of primary amines with dihalides using microreactors
(Chemical Equation Presented) A practical, rapid, and efficient reaction using microreactors for the direct N-alkylation from aniline derivatives and alkyl dihalides has been achieved in the presence of aqueous potassium carbonate at an elevated temperature. This improved synthetic methodology provides a straightforward microfluid approach to the synthesis of a variety of N-aryl azacycloalkanes. Copyright Taylor & Francis Group, LLC.
He, Hongjie,Lin, Qi,Liu, Xiaofeng,Yang, Yongtai,Zhou, Yaming,Jia, Yu,Gao, Xiang
experimental part
p. 2512 - 2525
(2012/07/14)