- Lewis acid-mediated cyclizations of (2'-amino-N'-tert-butoxycarbonyl- benzylidene)-3-alkenylamines
-
Depending on the method of activation, (2'-amino-N'-tert- butoxycarbonyl-benzylidene)-3-alkenylamines (1) react with Lewis acids (TiCl4 or TMSOTf) to afford either a novel Boc-assisted iminium ion formation/trapping sequence (giving hexahydropy
- Frank, Kristine E.,Aube, Jeffrey
-
-
Read Online
- Copper-promoted difunctionalization of unactivated alkenes with silanes
-
An efficient copper-catalyzed cascade difunctionalization of N-allyl anilines toward the synthesis of silylated indolines using commercially available silanes has been reported. This strategy provides a new avenue for the synthesis of a diverse array of i
- Chen, Xiaoyu,Guo, Zhuangzhuang,Li, Jingya,Wu, Yangjie,Wu, Yusheng,Xue, Yingying,Zou, Dapeng
-
supporting information
p. 989 - 994
(2022/02/11)
-
- Ultrasound promoted environmentally benign, highly efficient, and chemoselective N-tert-butyloxycarbonylation of amines by reusable sulfated polyborate
-
The sulfated polyborate catalyzed an efficient and chemoselective N-tert-butyloxycarbonylation of amines under ultrasonic irradiation is developed. A broad substrate scope has been demonstrated for N-Boc protection of various primary/secondary amines. It allows converting several aliphatic/aryl/heteroaryl amines, amino alcohol, aminoester, and chiral amines to their N-Boc-protected derivatives under solvent-free conditions with excellent yields. The protocol has several advantages such as easy catalyst, and product isolation, short reaction time, excellent yields, outstanding chemoselectivity, and catalyst recyclability, among others. This makes the process practicable, economical, and environmentally benign.
- Pise, Ashok S.,Ingale, Ajit P.,Dalvi, Navnath R.
-
supporting information
p. 3768 - 3780
(2021/10/26)
-
- Sulfated tungstate: A highly efficient, recyclable and ecofriendly catalyst for chemoselective N-tert butyloxycarbonylation of amines under the solvent-free conditions
-
Sulfated tungstate catalyzed an efficient and ecofriendly protocol has been described for the chemoselective N-tert-butyloxycarbonylation of amines under the solvent-free conditions at room temperature. The variety of functionalized aliphatic, aromatic and heteroaromatic amines efficiently undergoes the N-tert-butyloxycarbonylation under the developed protocol. The aminoalcohol, aminophenol, aminoester as well as various chiral amines underwent the chemoselective N-Boc protection under the optimized reaction condition. The rapid reaction rate, mild conditions, very good functional group tolerance, excellent yield, solvent-free, easy recovery products and excellent catalyst recyclability are the advantages of this protocol. This makes the protocol feasible, economical and environmentally benign.
- Ingale, Ajit P.,Shinde, Sandeep V.,Thorat, Nitin M.
-
supporting information
p. 2528 - 2543
(2021/07/02)
-
- Thiamine hydrochloride as a recyclable organocatalyst for the efficient and chemoselective N-tert-butyloxycarbonylation of amines
-
Thiamin hydrochloride promoted highly efficient and ecofriendly approach has been described for the chemoselective N-tert-butyloxycarbonylation of amines under solvent-free conditions at ambient temperature. The demonstrated approach has been applicable for the N-Boc protection of variety of aliphatic, aryl, heteroaryl amines. The chemoselective protection of amino group occurs in chiral amines and amino alcohol without racemization in high yield. Thiamin hydrochloride is stable, economical, easy to handle and environmentally friendly.
- Ingale, Ajit P.,Garad, Dnyaneshwar N.,Ukale, Dattatraya,Thorat, Nitin M.,Shinde, Sandeep V.
-
supporting information
p. 3791 - 3804
(2021/11/04)
-
- Nanoceria as an efficient and green catalyst for the chemoselective N-tert-butyloxycarbonylation of amines under the solvent-free conditions
-
Nanocerium oxide mediated an efficient and green protocol has been described for the chemoselective N-tert-butyloxycarbonylation of amines under the solvent-free conditions at ambient temperature. Various aliphatic, aromatic and heteroaromatic amines were protected using developed protocol and several functional groups such as alcohol, phenol and ester were well tolerated under these conditions. The rapid reaction rate, mild conditions, very good functional group tolerance, excellent yield, solvent-free, easy recovery products and excellent catalyst recyclability are the advantages of this protocol. This makes the protocol feasible, economical and environmentally benign.
- Garad, Dnyaneshwar N.,Ingale, Ajit P.,Shinde, Sandeep V.,Ukale, Dattatraya
-
supporting information
p. 1656 - 1668
(2021/04/05)
-
- Base-Mediated Generation of Ketenimines from Ynamides: [3+2] Annulation with Azaallyl Anions
-
Under basic conditions and heat, ynamides can serve as precursors to ketenimines, whose synthetic potential is often hampered by their difficulty of access. Herein, we report that they can undergo a [3+2] cycloaddition with 2-azaallyl anions, obtained from benzylimines under the same reaction conditions. This reaction between two highly reactive intermediates, both generated in situ from bench stable starting materials, gives access to various nitrogen-rich heterocycles. The reaction usually proceeds with excellent diastereoselectivity, in favor of the cis adduct. Deuteration experiments and DFT calculations helped rationalize the regio- and stereoselectivity of the process as well as the formation of side products. (Figure presented.).
- D'Hollander, Agathe C. A.,Romero, Eugénie,Vijayakumar, Kamsana,Le Houérou, Camille,Retailleau, Pascal,Dodd, Robert H.,Iorga, Bogdan I.,Cariou, Kevin
-
supporting information
p. 2903 - 2908
(2021/04/21)
-
- Integrating Hydrogen Production and Transfer Hydrogenation with Selenite Promoted Electrooxidation of α-Nitrotoluenes to E-Nitroethenes
-
Developing an electrochemical carbon-added reaction with accelerated kinetics to replace the low-value and sluggish oxygen evolution reaction (OER) is markedly significant to pure hydrogen production. Regulating the critical steps to precisely design electrode materials to selectively synthesize targeted compounds is highly desirable. Here, inspired by the surfaced adsorbed SeOx2? promoting OER, NiSe is demonstrated to be an efficient anode enabling α-nitrotoluene electrooxidation to E-nitroethene with up to 99 % E selectivity, 89 % Faradaic efficiency, and the reaction rate of 0.25 mmol cm?2 h?1 via inhibiting side reactions for energy-saving hydrogen generation. The high performance can be associated with its in situ formed NiOOH surface layer and absorbed SeOx2? via Se leaching-oxidation during electrooxidation, and the preferential adsorption of two -NO2 groups of intermediate on NiOOH. A self-coupling of α-carbon radicals and subsequent elimination of a nitrite molecule pathway is proposed. Wide substrate scope, scale-up synthesis of E-nitroethene, and paired productions of E-nitroethene and hydrogen or N-protected aminoarenes over a bifunctional NiSe electrode highlight the promising potential. Gold also displays a similar promoting effect for α-nitrotoluene transformation like SeOx2?, rationalizing the strategy of designing materials to suppress side reactions.
- Chong, Xiaodan,Liu, Cuibo,Wang, Changhong,Yang, Rong,Zhang, Bin
-
supporting information
p. 22010 - 22016
(2021/09/02)
-
- Highly efficient chemoselective N-tert butoxycarbonylation of aliphatic/aromatic/heterocyclic amines using diphenylglycoluril as organocatalyst
-
An efficient approach for the Chemoselective N-tert-butoxycarbonylation of a variety of amines using diphenylglycoluril as organocatalyst has been described. For the first time, a plausible mechanism for the N-tert-butoxycarbonylation has been proposed using density functional theory (DFT) calculations supported by NMR studies. The reusability of the organocatalyst and observation of the desired N-Boc protected amines being formed without the formation of side products like urea, oxazolidinone, isocyanate, and N, N-di-Boc derivatives makes the present protocol desirable.
- Awasthi, Amardeep,Mukherjee, Anagh,Singh, Mandeep,Rathee, Garima,Vanka, Kumar,Chandra, Ramesh
-
-
- PRODUCTION METHOD FOR AMIDATE COMPOUND
-
A method for producing an amidate compound represented by Formula (3), comprising reacting a urethane compound represented by Formula (1) with a carboxylate compound represented by Formula (2): (in the formulas, A, n, R1, R2, R3, R4, R5, R6, X, and a are as described in the Description).
- -
-
Paragraph 0126-0128
(2020/02/13)
-
- Amidate compound, catalyst for polyurethane production, and method for producing polyurethane resin
-
Provided is an amidate compound represented by the formula (1): wherein A is a substituted or unsubstituted hydrocarbon group, n is an integer of 1 or more, and D is a nitrogen-containing organic group represented by the formula (2): wherein R1, R2, and R3 are the same or different, and are each a hydrocarbon group that may contain a heteroatom; some or all of R1, R2, and R3 may be bonded together to form a ring structure; X is a nitrogen atom, an oxygen atom, or a sulfur atom; and a is 0 or 1, wherein a is 1 when X is a nitrogen atom, and a is 0 when X is an oxygen atom or a sulfur atom.
- -
-
Page/Page column 123
(2020/07/09)
-
- Cu-Mediated Synthesis of Indolines and Dihydroisoquinolinones through Arylperfluoroalkylation of Unactivated Alkenes
-
The copper-mediated fluroalkylation/cyclization of N-allyl anilines has been described using fluoroalkyl iodides as fluoroalkylation reagents for the first time. The reaction provides an efficient and direct access to 3-fluoroalkyl indolines in moderate to good yields with unactivated double bonds as the radical acceptor. This protocol combines a simple experimental procedure with low-costing fluoroalkylated sources and excellent functional group tolerance.
- Li, Dandan,Wang, Yan,Jia, Zhenzhen,Ou, Zhaocheng,Dong, Yongrui,Lv, Cunjie,Fu, Guangbin,Liang, Deqiang
-
p. 4797 - 4804
(2019/08/12)
-
- Aryltrifluoromethylative cyclization of unactivated alkenes by the use of PhICF3Cl under catalyst-free conditions
-
A concise and catalyst-free aryltrifluoromethylative cyclization of unactivated alkenes has been developed herein. The use of PhICF3Cl as a powerful trifluoromethylating agent allows easy transformations. A set of trifluoroethylated carbocycles and aza-hereocycles were efficiently synthesized in good yield and selectivity. A broad substrate scope, mild reaction conditions, and easy operation would make this method well-suited for applications.
- Guo, Jia,Xu, Cong,Liu, Xiaowei,Wang, Mang
-
supporting information
p. 2162 - 2168
(2019/02/27)
-
- A new bifunctional heterogeneous nanocatalyst for one-pot reduction-Schiff base condensation and reduction-carbonylation of nitroarenes
-
In this work, synthesis of Pd-NHC-γ-Fe2O3-n-butyl-SO3H and its activity as a bifunctional heterogeneous nanocatalyst containing Pd-NHC and acidic functional groups, are described. This newly synthesized nanomagnetic catalyst is fully characterized by different methods such as FT-IR, XPS, TEM, VSM, ICP and TG analysis. At first, the catalytic activity of Pd-NHC-γ-Fe2O3-n-butyl-SO3H is evaluated for the reduction of nitroarenes in aqueous media using NaBH4 as a clean source of hydrogen generation at ambient temperature. Using the promising results obtained from the nitroarene reduction, this catalytic system is used for two one-pot protocols including reduction-Schiff base condensation and reduction-carbonylation of various nitroarenes. In these reactions the in situ formed amines are further reacted with aldehydes to yield imines or carbonylated to amides. The desired products are obtained in good to high yields in the presence of Pd-NHC-γ-Fe2O3-n-butyl-SO3H as a bifunctional catalyst. The catalyst is reused with the aid of a magnetic bar for up to six consecutive cycles without any drastic loss of its catalytic activity.
- Sobhani, Sara,Chahkamali, Farhad Omarzehi,Sansano, José Miguel
-
p. 1362 - 1372
(2019/01/24)
-
- Oxo-bridge bicyclo-[2.2.1]-heptene compound containing boric acid derived group as well as synthesis method and application thereof
-
The invention discloses an oxo-bridge bicyclo-[2.2.1]-heptene compound containing a boric acid derived group as well as a synthesis method and application thereof. A target compound disclosed by the invention is prepared from 3-(4-hydroxylphenyl)-4-(4-boratephenyl)-furan and an ethylene sulfonamide derivative through Diels-Alder reaction and subsequent hydrolysis reaction. The oxo-bridge bicyclo-[2.2.1]-heptene compound has the advantages of relatively high reaction total yield, mild conditions and high speed. An in-vivo experiment proves that compared with an existing breast-cancer-resistingmedicine 4-hydroxytamoxifen (4-OHT), the novel oxo-bridge bicyclo-[2.2.1]-heptene compound containing the boric acid derived group has a higher inhibition effect on proliferation of hormone-dependingbreast cancer MCF-7 cells.
- -
-
Paragraph 0093-0096; 0103
(2018/12/02)
-
- METHOD FOR THE MANUFACTURE OF EFAVIRENZ
-
This invention relates to a method for the manufacture of optically pure (S)-6- chloro-(cyclopropylethynyl)-1,4-dihydro-4-(trifluoromethyl)-2H-3,1 -benzoxazin- 2-one. Specifically, this invention relates to a flow synthesis method for the manufacture of (S)-6-chloro-(cyclopropylethynyl)-1,4-dihydro-4- (trifluoromethyl)-2H-3,1 -benzoxazin-2-one.
- -
-
Page/Page column 11; 25; 26
(2018/09/19)
-
- Chemoselective: N-tert -butyloxycarbonylation of amines in glycerol
-
A catalyst-free, efficient and green protocol has been developed for the chemoselective N-Boc protection of amines by using glycerol as a solvent at room temperature. A variety of functionalized amines, such as aliphatic, aromatic as well as heteroaromatic were protected using the developed protocol. N-tert-Butyloxycarbonylation derivatives were formed without the formation of isocyanate, urea, N,N-di-t-Boc, or oxazolidinone as side products. The operational simplicity, cleaner reaction, rapid reaction convergence, functional group tolerance, excellent yield, high selectivity, catalyst-free feature and solvent recyclability are the distinct advantages of this protocol. Owing to these merits, this protocol is feasible, economical and environmentally benign.
- Ingale, Ajit P.,More, Vishal K.,Gangarde, Uddhav S.,Shinde, Sandeep V.
-
supporting information
p. 10142 - 10147
(2018/06/18)
-
- Quinolinones as Inhibitors of Translation Initiation Complex
-
Provided herein are compounds and pharmaceutical compositions comprising quinolinones. The quinolinones and compositions thereof are useful as eukaryotic translation initiation factor 4F (eIF4F) complex modulators.
- -
-
Paragraph 0477
(2018/03/25)
-
- One-pot synthesis of polyfunctionalized quinolines: Via a copper-catalyzed tandem cyclization
-
An efficient one-pot approach for the synthesis of polyfunctionalized quinolines was developed via a sequence of copper-catalyzed coupling reaction/propargyl-allenyl isomerization/aza-electrocyclization. Easily available starting materials, mild conditions, and a wide substrate scope make this approach potentially useful.
- Chen, Dianpeng,Sun, Xuejun,Shan, Yingying,You, Jinmao
-
supporting information
p. 7657 - 7662
(2018/11/02)
-
- Selective Oxidative Coupling Reaction of Isocyanides Using Peroxide as Switchable Alkylating and Alkoxylating Reagent
-
A switchable oxidative coupling reaction of isocyanide and peroxide has been disclosed. In the presence of iron catalyst, the coupling reaction affords N-arylacetamides in good yields. By simply replacing the iron with copper catalyst, another different coupling reaction takes place in which peroxide can serve as alkoxylating source. This protocol represents a new fundamental coupling of two basic chemicals involving C?C and C?O bond-forming process. The unusual reactivity of an isocyano group in a radical reaction acting formally as an amidoyl synthon has also been well established. The experiment outcome reveals that aromatic isocyanides are particularly compatible reaction partners in present coupling reaction, whereas no desired products are observed when aliphatic isocyanides are used. (Figure presented.).
- Zhang, Xinglu,Liu, Zhiqiang,Gao, Yu,Li, Feng,Tian, Yaming,Li, Chunju,Jia, Xueshun,Li, Jian
-
supporting information
p. 272 - 277
(2017/11/13)
-
- A highly efficient heterogeneous copper-catalyzed chlorodeboronation of arylboronic acids leading to chlorinated arenes
-
A highly efficient heterogeneous copper-catalyzed chlorodeboronation of arylboronic acids with inexpensive N-chlorosuccinimide (NCS) was achieved in MeCN in the presence of 10 mol% of l-proline-functionalized MCM-41-immobilized copper(i) complex [MCM-41-l-proline-CuCl] under mild conditions, yielding a variety of aryl chlorides in excellent yields. This method proved to be tolerant of a broad range of functional groups and particularly useful for the conversion of electron-deficient arylboronic acids to aryl chlorides, a transformation that is inefficient without copper catalysis. This heterogeneous copper catalyst can be recovered by a simple filtration of the reaction solution and recycled for at least 10 times without any decreases in activity.
- He, Wen,Zhang, Rongli,Cai, Mingzhong
-
p. 764 - 770
(2017/01/13)
-
- Efficient and expeditious chemoselective BOC protection of amines in catalyst and solvent-free media
-
A green and eco-friendly route for the almost quantitative BOC protection of a large variety of aliphatic and aromatic amines, amino acids, and amino alcohols is reported in catalyst and solvent-free media under mild reaction conditions. The products were confirmed by 1H, 13C NMR, IR spectroscopy, and in some cases, elemental analysis. This protocol does not require any water quenches, solvent separations, and purification steps, such as recrystallization and column chromatography.
- Viswanadham, Balaga,Mahomed, Abdul S.,Friedrich, Holger B.,Singh, Sooboo
-
p. 1355 - 1363
(2017/02/15)
-
- Harnessing Cascade Suzuki-Cyclization Reactions of Pyrazolo[3,4-b]pyridine for the Synthesis of Tetracyclic Fused Heteroaromatics
-
Numerous procedures have been described for the functionalization of pyrazolo[3,4-b]pyridine, mainly involving nucleophilic substitutions at the C-4 position or esterifications/amidations at the C-5 position. In this paper, we describe a robust, easy to implement protocol for the Suzuki cross-coupling reaction of chloroarene 2, followed by in-situ lactonization to provide chromenopyrazolopyridines. The extension of the scope of the reaction to fused naphthyridinones is also reported. This strategy gave access to 10 original pyrazolopyridine-containing tetracyclic compounds.
- Lavrard, Hubert,Popowycz, Florence
-
supporting information
p. 600 - 608
(2017/02/05)
-
- Preparation, characterization and application of 1,4-disulfopiperazine-1,4-diium chloride ([Piper-(SO3H)2]·2Cl) as an efficient dicationic ionic catalyst for the N-Boc protection of amines
-
In this work, 1,4-disulfopiperazine-1,4-diium chloride ([Piper-(SO3H)2]·2Cl), as a novel Br?nsted acidic ionic catalyst is synthesized and characterized using a series of techniques including FT-IR, TGA, DTA, SEM, pH analysis and Hammett acidity function. This substance can significantly catalyze the N-Boc protection of amines without solvent interference at room temperature. The advantages of this manner are chemoselectivity, short reaction times, suitable yields, excellent yields of the products, without solvent interference and ease of preparation as well as reusability of the catalyst.
- Koodehi, Tahereh Ghauri,Shirini, Farhad,Goli-Jolodar, Omid
-
p. 443 - 456
(2017/01/10)
-
- Sustainable and chemoselective N-Boc protection of amines in biodegradable deep eutectic solvent
-
Abstract: A green and practical approach for the chemoselective N-tert-butyloxycarbonylation of structurally diverse amines with di-tert-butyl dicarbonate (Boc2O) is described. Selective N-Boc protection was achieved in excellent yields in urea-choline chloride deep eutectic solvent (DES) as the most promising environmentally benign and cost-effective solvent under mild reaction condition. DES can protect various aromatic and aliphatic amines using Boc2O in good to excellent yields in short reaction times without any side products. Graphical abstract: [Figure not available: see fulltext.].
- Azizi, Najmedin,Shirdel, Fatemeh
-
p. 1069 - 1074
(2017/05/12)
-
- PVP-Pd nanoparticles as efficient catalyst for nitroarene reduction under mild conditions in aqueous media
-
The catalytic activity of PVP-Pd nanoparticles synthesized by electrochemical methods was explored in nitroaromatic hydrogenation reaction. In this transformation, the colloidal nanocatalyst proved to have outstanding catalytic activity under sustainable reaction conditions. This mild process efficiently reduced the nitroaromatic group at room temperature, without high pressure of molecular hydrogen and in aqueous medium. Furthermore, several functional groups were tolerated, given the corresponding substituted arylamines in excellent yields and with high TOF. In addition, one-pot reactions and tandem process were explored, in which nitroaromatic hydrogenation reaction was included in the synthesis of modified amines. This methodology was effectively incorporated in tandem reactions and one-pot procedures, achieving N-arylamines functionalized in good isolated yields. Finally, comparison of sustainable chemistry metrics analysis demonstrated that this methodology is a reliable approach to perform the nitro compound hydrogenation process.
- Uberman, Paula M.,García, Carolina S.,Rodríguez, Julieta R.,Martín, Sandra E.
-
supporting information
p. 739 - 748
(2017/05/19)
-
- Teaching Old Compounds New Tricks: DDQ-Photocatalyzed C?H Amination of Arenes with Carbamates, Urea, and N-Heterocycles
-
The C?H amination of benzene derivatives was achieved using DDQ as photocatalyst and BocNH2 as the amine source under aerobic conditions and visible light irradiation. Electron-deficient and electron-rich benzenes react as substrates with moderate to good product yields. The amine scope of the reaction comprises Boc-amine, carbamates, pyrazoles, sulfonimides and urea. Preliminary mechanistic investigations indicate arene oxidation by the triplet of DDQ to radical cations with different electrophilicity and a charge transfer complex between the amine and DDQ as intermediate of the reaction.
- Das, Somnath,Natarajan, Palani,K?nig, Burkhard
-
supporting information
p. 18161 - 18165
(2017/12/28)
-
- Efficient N-Boc protection of amines by a reusable heterogeneous solid acid nanocatalyst at room temperature
-
An efficient and rapid protocol for chemoselective N-Boc protection of various structurally different aryl, aliphatic, and heterocyclic amines is reported with (Boc)2O using mesoporous silica phenylsulfonic acid (SBA-15-Ph-SO3H) as a recyclable and heterogeneous solid acid nanocatalyst under solvent-free condition at ambient temperature. The catalyst can be easily recovered and reused for ten reaction cycles for protection of amines without considerable loss of activity. The advantages of this green method are simplicity, easy workup, chemoselectivity, short reaction time, and excellent yield.
- Veisi, Hojat,Sedrpoushan, Alireza,Ghazizadeh, Habibollah,Hemmati, Saba
-
p. 1451 - 1461
(2016/04/26)
-
- Pd(II)/Ag(I)-Promoted One-Pot Synthesis of Cyclic Ureas from (Hetero)Aromatic Amines and Isocyanates
-
A simple and facile one-pot reaction has been developed to afford a diverse range of N,N′-disubstituted benzimidazolones and imidazopyridinones containing two differently substituted N atoms. A cooperative Pd(II)/Ag(I) system promotes the sequential addition/intramolecular C-H amidation reaction of (hetero)aromatic amines and isocyanates, leading to the formation of two C-N bonds. A mechanism involving radical intermediates generated by single-electron transfer (SET) in the presence of a Ag2CO3 oxidant and Pd(OAc)2 Lewis acid is proposed. This protocol offers an operationally easy, simple, and robust approach with the use of readily available starting materials, good functional group tolerance, and high efficiency.
- Youn, So Won,Kim, Yi Hyun
-
supporting information
p. 6140 - 6143
(2016/12/09)
-
- Highly ortho-Selective Chlorination of Anilines Using a Secondary Ammonium Salt Organocatalyst
-
An organocatalytic, highly facile, efficient, and regioselective ortho-chlorination of anilines is described. A secondary ammonium chloride salt has been employed as the catalyst and the reaction can be conducted at room temperature without protection from air and moisture. In addition, the reaction is readily scalable and the catalyst can be recycled and reused. This catalytic protocol has been applied to the efficient synthesis of a highly potent c-Met kinase inhibitor. Mechanistic studies revealed that unique structural features of the secondary ammonium chloride salt are important for both the catalysis and regioselectivity of the electrophilic ortho-chlorination.
- Xiong, Xiaodong,Yeung, Ying-Yeung
-
supporting information
p. 16101 - 16105
(2016/12/26)
-
- Palladium-Catalyzed Decarboxylative Synthesis of Arylamines
-
A novel approach has been developed for the synthesis of arylamines via the palladium-catalyzed intramolecular decarboxylative coupling (IDC) of aroyloxycarbamates, obtained in situ by reacting aryl carboxylic acids with hydroxycarbamates. The reaction offers facile access to structurally diverse arylamines with the site-specific formation of the C(sp2)-N bond under mild conditions.
- Dai, Qipu,Li, Peihe,Ma, Nuannuan,Hu, Changwen
-
p. 5560 - 5563
(2016/11/17)
-
- Palladium-catalyzed oxidative carbonylation of aromatic C-H bonds of N -alkylanilines with CO and alcohols for the synthesis of o -aminobenzoates
-
A Pd(II)-catalyzed C-H monocarbonylation of N-alkylanilines for the synthesis of o-aminobenzoates has been developed. Various aliphatic alcohols and phenol were tolerated in the reaction to afford the corresponding o-aminobenzoates in good yields under mild balloon pressure of CO.
- Chen, Ming,Ren, Zhi-Hui,Wang, Yao-Yu,Guan, Zheng-Hui
-
p. 1258 - 1263
(2015/01/30)
-
- Benzothiazepine CGP37157 and its 2′-isopropyl analogue modulate Ca2+ entry through CALHM1
-
CALHM1 is a Ca2+ channel discovered in 2008, which plays a key role in the neuronal electrical activity, among other functions. However, there are no known efficient blockers able to modulate its Ca2+ handling ability. We herein desc
- Moreno-Ortega, Ana J.,Martínez-Sanz, Francisco J.,Lajarín-Cuesta, Rocío,De Los Rios, Cristóbal,Cano-Abad, María F.
-
p. 503 - 510
(2015/06/17)
-
- A practical lewis base catalyzed electrophilic chlorination of arenes and heterocycles
-
A mild phosphine sulfide catalyzed electrophilic halogenation of arenes and heterocycles that utilizes inexpensive and readily available N-halosuccinimides is disclosed. This methodology is shown to efficiently chlorinate diverse aromatics, including simple arenes such as anthracene, and heterocycles such as indoles, pyrrolopyrimidines, and imidazoles. Arenes with Lewis acidic moieties also proved amenable, underscoring the mild nature of this chemistry. Lewis base catalysis was also found to improve several diverse aromatic brominations and iodinations.
- Maddox, Sean M.,Nalbandian, Christopher J.,Smith, Davis E.,Gustafson, Jeffrey L.
-
supporting information
p. 1042 - 1045
(2015/03/30)
-
- Direct Amidation of N-Boc- and N-Cbz-Protected Amines via Rhodium-Catalyzed Coupling of Arylboroxines and Carbamates
-
N-Boc- and N-Cbz-protected amines are directly converted into amides by a novel rhodium-catalyzed coupling of arylboroxines and carbamates, replacing the traditional two-step deprotection-condensation sequence. Both protected anilines and aliphatic amines are efficiently transformed into a wide variety of secondary benzamides, including sterically hindered and electron-deficient amides, as well as in the presence of acid-labile and reducible functional groups.
- Lim, Diane S. W.,Lew, Tedrick T. S.,Zhang, Yugen
-
supporting information
p. 6054 - 6057
(2016/01/09)
-
- Installation of protected ammonia equivalents onto aromatic & heteroaromatic rings in water enabled by micellar catalysis
-
A single set of conditions consisting of a palladium catalyst, a commercially available ligand, and a base, allow for several types of C-N bond constructions to be conducted in water with the aid of a commercially available "designer" surfactant (TPGS-750-M). Products containing a protected NH2 group in the form of a carbamate, sulfonamide, or urea can be fashioned starting with aryl or heteroaryl bromides, iodides, and in some cases, chlorides, as substrates. Reaction temperatures are in the range of room temperature to, at most, 50 °C, and result in essentially full conversion and good isolated yields.
- Isley, Nicholas A.,Dobarco, Sebastian,Lipshutz, Bruce H.
-
supporting information
p. 1480 - 1488
(2014/03/21)
-
- N-Protection of amines using pyridinium 2,2,2-trifluoroacetate ionic liquid as an efficient and reusable catalyst
-
A simple, green, and efficient method for the N-tert-butoxycarbonylation of amines by pyridinium 2,2,2-trifluoroacetate ([Py][OTf]) as an efficient and reusable catalyst is reported. In general, electron donating groups on aryl group give rise to the higher yields than electron withdrawing groups. Clean reaction, short reaction times, high yields, reusability of catalyst, and easy preparation of it are some advantages of this work.
- Karimian, Somaye,Tajik, Hassan
-
p. 218 - 220
(2014/02/14)
-
- Water at elevated temperatures (WET): Reactant, catalyst, and solvent in the selective hydrolysis of protecting groups
-
Water at elevated temperatures (WET) can act simultaneously as reactant, solvent, and catalyst in reaction processes. WET has been successfully employed in the removal of protecting groups alleviating the need for added strong acids/bases, subsequent neutralization and waste salt elimination. The protocols for the water-mediated removal of several common protecting groups such as tert-butyl carbamates (N-Boc) from 125 to 150 °C, acetamide (N-Ac) at 275 °C and acetate esters (O-Ac) at 250 °C are reported for different model aryl compounds. In addition, high yields and selective deprotection of one protecting group in the presence of another by simply tuning the temperature is demonstrated. In order to gain further insights into reaction processes, the aqueous solubilities of several of the reactants, the kinetics and mechanisms associated with some of these reactions are also discussed. the Partner Organisations 2014.
- Medina-Ramos, Wilmarie,Mojica, Mike A.,Cope, Elizabeth D.,Hart, Ryan J.,Pollet, Pamela,Eckert, Charles A.,Liotta, Charles L.
-
p. 2147 - 2155
(2014/04/17)
-
- A 2,6-bis(phenylamino)pyridinato titanium catalyst for the highly regioselective hydroaminoalkylation of styrenes and 1,3-butadienes
-
The C-C bond forming catalytic hydroaminoalkylation of terminal alkenes, 1,3-dienes, or styrenes allows a direct and highly atom efficient (100 %) synthesis of amines which can result in the formation of two regioisomers, the linear and the branched product. We present a new titanium catalyst with 2,6-bis(phenylamino)pyridinato ligands for intermolecular hydroaminoalkylation reactions of styrenes and 1-phenyl-1,3-butadienes that delivers the corresponding linear hydroaminoalkylation products with excellent regioselectivities. Linear progress: A new Ti complex with 2,6-bis(phenylamino) pyridinato ligands catalyzes highly regioselective hydroaminoalkylation reactions of styrenes. The process that directly gives access to the corresponding linear hydroaminoalkylation products offers a new and flexible synthetic approach towards pharmaceutically important 3-arylpropylamines. It is also possible to convert (E)-1-phenyl-1,3-butadienes into the corresponding linear products.
- Doerfler, Jaika,Preuss, Till,Schischko, Alexandra,Schmidtmann, Marc,Doye, Sven
-
supporting information
p. 7918 - 7922
(2014/08/05)
-
- Metal free oxidative coupling of aryl formamides with alcohols for the synthesis of carbamates
-
A direct transformation of N-aryl formamides to the corresponding carbamates via the formation of isocyanate intermediates is achieved in good yields using hypervalent iodine as an oxidant. This journal is
- Reddy, N. Veera,Prasad, K. Rajendra,Reddy, P. Sudhir,Lakshmi Kantam,Reddy, K. Rajender
-
supporting information
p. 2172 - 2175
(2014/04/03)
-
- INHIBITORS OF THE MITF MOLECULAR PATHWAY
-
Provided herein are compounds of the formula (IV) as well as pharmaceutically acceptable salts thereof, wherein the substituents are as those disclosed in the specification. These compounds, and the pharmaceutical compositions containing them, are useful as MITF inhibitors, MITF pathway inhibitors and for the treatment of cancer.
- -
-
Paragraph 00179
(2015/01/09)
-
- Nano-ferrous ferric oxide (nano-Fe3O4): Powerful, reusable, and stable catalyst for N-Boc protection of amines
-
Nano-ferrous ferric oxide (nano-Fe3O4) efficiently catalyzed N-boc protection of amines in high yields and acceptable reaction times. Nano-Fe3O4 was applied as an efficient, green, heterogeneous and reusable magnetite catalyst. Clean reaction, simple purification, short reaction time and high yield were some other advantages of this compound.
- Zolfigol, Mohammad Ali,Moosavi-Zare, Ahmad Reza,Moosavi, Parvin,Khakyzadeh, Vahid,Zare, Abdolkarim
-
p. 962 - 966
(2013/11/06)
-
- Iron(III)triflate as a highly efficient, recyclable and green catalyst for the N-Boc protection of amines
-
Iron (III) triflate was used as an efficient catalyst for N-t-butoxycarbonylation of amines with di-t-butyl dicarbonate under solvent-free conditions at room temperature. Various aliphatic, aromatic, heterocyclic amines and aminols were protected as their corresponding mono-carbamates in excellent yields and short reaction times. Only two of the 23 monocarbamates were new. No competitive side reactions such as isocyanate, urea, nor N,N-di-Boc formation were observed. The reported method is mild and has the advantages of low cost, chemoselectivity and, because no solvent is used and the catalyst can be recycled, it is classifiable as a green procedure.
- Feng, Chengliang,Chu, Ningning,Zhang, Shuguang,Cai, Jin,Chen, Junqing,Hu, Huayou,Ji, Min
-
p. 757 - 760
(2014/01/23)
-
- Solvent free N-Boc protection of amines using amberlystr a 21 solid base resin as a reusable heterogeneous catalyst
-
An efficient, environmentally benign, highly facile and convenient synthetic protocol for the selective t-butyl carboxylation of aliphatic, aromatic and heterocyclic amines using AmberlystR A 21 catalyst; a mild basic solid resin under solvent free conditions is reported. This method explores several advantages such as reusability of the heterogeneous catalyst, cleaner reaction profile, mild and solvent free system, short reaction time, operational simplicity, high conversions , excellent product yields and low cost of the catalyst. Furthermore since the catalyst is mild basic, decomposition of the carbamate formed is not observed if the reaction is continued for prolonged time as in the case of Lewis acid catalyzed N-Boc protection. This makes the present protocol a useful and attractive for N-Boc protection of amines.
- Tekale, Sunil U.,Kauthale, Sushama S.,Pawar, Rajendra P.
-
p. 1619 - 1623
(2013/09/12)
-
- {[[K.18-Crown-6]Br3}n: A tribromide catalyst for the catalytic protection of amines and alcohols
-
{[K.18-Crown-6]Br3}n, a unique tribromide-type catalyst, was utilized for the N-boc protection of amines and trimethylsilylation (TMS) and tetrahydropyranylation (THP) of alcohols. The method is general for the preparation of N-boc derivatives of aliphatic (acyclic and cyclic) and aromatic, and primary and secondary amines and also various TMS-ethers and THP-ethers. The simple separation of the catalyst from the product is one of the many advantages of this method.
- Chehardoli, Gholamabbas,Zolfigol, Mohammad Ali,Derakhshanpanah, Fateme
-
p. 1730 - 1733
(2013/10/21)
-
- A mild and green method for the N-BOC protection of amines without assistant of catalyst under solvent-free conditions
-
A facile, green and versatile method for the Boc protection of amines has been developed by a treatment with (Boc)2O without any additive at room temperature. The method is general for the preparation of N-Boc derivatives of aliphatic (acyclic and cyclic), aromatic, and heteroaromatic amines; primary and secondary amines. The advantages of this method are green, simplicity, short reaction times and excellent yields.
- Mojtahedi, Mohammad Majid,Niknejad, Nina,Veisi, Hojat
-
p. 121 - 125
(2013/07/26)
-
- Synthesis, characterization and catalytic properties of monodispersed nano-sphere silica sulfuric acid
-
In this research, the first report on synthesis of nano-sphere silica sulfuric acid (NS-SSA) as new catalyst was reported. The catalyst was prepared by the reaction of nano-sphere silica with chlorosulfonic acid at room temperature. The catalyst has been identified using various techniques (XRD, SEM, TEM, EDX, TGA, FT-IR) and results were shown that it was a spherical shape and its particle size was between 60 and 90 nm. The catalyst can be easily recovered and reused for seventeen reaction cycles for protection of amines without considerable loss of activity. It was found that the catalyst can be efficiently in large scale and we examined some reactions in scales of 50 and 100 mmol. Also, this method has some advantages such as high TOF of catalyst, chemoselectivity, easy work-up and short reaction time.
- Zolfigol,Khazaei,Mokhlesi,Derakhshan-Panah
-
p. 111 - 116
(2013/04/23)
-
- Magnetic nanoparticles catalyzed N-tert-butoxycarbonylation of Amines and amine derivatives
-
A simple and efficient protocol for the chemoselective mono-N-Boc protection of various structurally diverse amines with di-tert-butyl dicarbonate using magnetically recoverable γ-Fe2O3@SiO 2 nanoparticles is reported. The catalyst can be easily recovered and recycled without a significant loss in the catalytic activity. No competitive side reactions, such as formation of isocyanate, urea, oxazolidinone, and N,N-di-Boc derivatives were obsereved.
- Akbari, Jafar,Sajirani, Soghra B.,Nezhad, Jafar M.,Heydari, Akbar
-
experimental part
p. 165 - 168
(2012/07/14)
-
- Microwave assisted mild, rapid, solvent-less, and catalyst-free chemoselective N-tert-butyloxycarbonylation of amines
-
Microwave assisted simple, rapid, solventless, and catalyst-free chemoselective method for the protection of amino group in aromatic, aliphatic, heterocyclic, aralkyl amines, phenyl hydrazine, and amino acid esters in good to excellent isolated yield (83-98%) in short reaction time (2-12 min) has been reported.
- Dighe, Satish N.,Jadhav, Hemant R.
-
p. 5803 - 5806
(2012/10/29)
-
- Simple and efficient method for n-boc protection of amines using PEG-400 as a reaction medium under mild conditions
-
Simple and efficient method for N-Boc protection of amines using PEG-400 as an ecofriendly reaction medium at room temperature is described. Various aromatic, heteroaromatic, and aliphatic amines were converted to the corresponding N-tert-butyl-carbamates in good to excellent yields in short times.
- Zeng, Hongyao,Li, Yongjia,Shao, Huawu
-
experimental part
p. 25 - 32
(2011/10/19)
-
- Outer-sphere direction in iridium C-H borylation
-
The NHBoc group affords ortho selective C-H borylations in arenes and alkenes. Experimental and computational studies support an outer sphere mechanism where the N-H proton hydrogen bonds to a boryl ligand oxygen. The regioselectivities are unique and com
- Roosen, Philipp C.,Kallepalli, Venkata A.,Chattopadhyay, Buddhadeb,Singleton, Daniel A.,Maleczka, Robert E.,Smith, Milton R.
-
supporting information; experimental part
p. 11350 - 11353
(2012/08/29)
-