- NMR studies of hydrogen bonding inte1ractions with secondary amide and urea groups
-
The cis/trans ratios for six model secondary amides were determined by 1H NMR in a range of solvent systems. The trans to cis equilibrium in chloroform is only slightly affected by addition of the hydrogen bond donor, trifluorethanol, but the c
- Deetz, Martin J.,Fahey, Julianne E.,Smith, Bradley D.
-
-
Read Online
- Enantioselective Synthesis of Azetidines through [3 + 1]-Cycloaddition of Donor-Acceptor Aziridines with Isocyanides
-
The enantioselective [3 + 1]-cycloaddition of racemic donor-acceptor (D-A) aziridines with isocyanides was first realized under mild reaction conditions using a chiral N,N′-dioxide/MgIIcomplex as catalyst, providing a facile route to enantioenriched exo-imido azetidines with good to excellent yield (up to 99%) and enantioselectivity (up to 94% ee). An obvious chiral amplification effect was observed in this system, and an explanation was elucidated based on the experimental investigation and X-ray crystal structure of the enantiomerically pure catalyst.
- Zhang, Fengcai,Sang, Xinpeng,Zhou, Yuqiao,Cao, Weidi,Feng, Xiaoming
-
supporting information
p. 1513 - 1517
(2022/03/01)
-
- Novel 4-phenoxypyridine derivatives bearing imidazole-4-carboxamide and 1,2,4-triazole-3-carboxamide moieties: Design, synthesis and biological evaluation as potent antitumor agents
-
Two series of novel 4-phenoxypyridine derivatives containing imidazole-4-carboxamide and 4-methyl-5-oxo-4,5-dihydro-1,2,4-triazole-3-carboxamide moieties were synthesized and evaluated for their in vitro inhibitory activities against c-Met kinase and anti
- Chen, Ye,Ding, Shi,Du, Siyuan,Hou, Yunlei,Li, Chunyan,Li, Zhen,Liu, Fang,Liu, Ju,Shen, Jiwei,Wang, Huan,Wei, Hao,Wu, Shuang
-
-
- Preparation and catalytic evaluation of a palladium catalyst deposited over modified clinoptilolite (Pd&at;MCP) for chemoselective N-formylation and N-acylation of amines
-
Novel palladium nanoparticles stabilized by clinoptilolite as a natural inexpensive zeolite prepared and used for N-formylation and N-acylation of amines at room temperature at environmentally benign reaction conditions in good to excellent yields. Pd (II) was immobilized on the surface of clinoptilolite via facile multi-step amine functionalization to obtain a sustainable, recoverable, and highly active nano-catalyst. The structural and morphological characterizations of the catalyst carried out using XRD, FT-IR, BET and TEM techniques. Moreover, the catalyst is easily recovered using simple filtration and reused for 7 consecutive runs without any loss in activity.
- Amirsoleimani, Mina,Khalilzadeh, Mohammad A.,Zareyee, Daryoush
-
-
- Reversible switching between housane and cyclopentanediyl isomers: An isonitrile-catalysed thermal reverse reaction
-
The photo-isomerization of an isolable five-membered singlet biradical based on C, N, and P ([TerNP]2CNDmp, 2a) selectively afforded a closed-shell housane-type isomer (3a) by forming a transannular P-P bond. In the dark, the housane-type species re-isomerized to the biradical, resulting in a fully reversible overall process. In the present study, the influence of tBuNC on the thermal reverse reaction was investigated: The isonitrile acted as a catalyst, thus allowing control over the thermal reaction rate. Moreover, tBuNC also reacted with the biradical to form an adductspecies ([TerNP]2CNDmp·CNtBu, 4a), which can be regarded as the resting state of the system. The reactive species 2a and 3a could be re-generated in situ by irradiation with red light. The results of this study extend our understanding of this new class of molecular switches.
- Beer, Henrik,Bresien, Jonas,Michalik, Dirk,Schulz, Axel,Villinger, Alexander
-
supporting information
p. 13986 - 13992
(2020/11/02)
-
- Mild C?F Activation in Perfluorinated Arenes through Photosensitized Insertion of Isonitriles at 350 nm
-
Fluorinated compounds have become important in the fields of agrochemical industry, pharmaceutical chemistry and materials sciences. Accordingly, various methods for their preparation have been developed in the past. Fluorinated compounds can be accessed via conjugation with fluorinated building blocks, via C?H fluorination or via selective activation of perfluorinated compounds to give the partially fluorinated congeners. Especially the direct activation of C?F bonds, one of the strongest σ-bonds, still remains challenging and new strategies for C?F activation are desirable. Herein a method for the photochemical activation of aromatic C?F bonds is presented. It is shown that isonitriles selectively insert into aromatic C?F bonds while aliphatic C?F bonds remain unaffected. Mechanistic studies reveal the reaction to proceed via the indirect excitation of the isonitrile to its triplet state by photoexcited acetophenone at 350 nm. Due to the relatively mild light used, the process shows high functional group tolerance and various compounds of the class of benzimidoyl fluorides are accessible from aryl isonitriles and commercially available perfluorinated arenes. (Figure presented.).
- Weidlich, Frauke,Esumi, Naoto,Chen, Dongyang,Mück-Lichtenfeld, Christian,Zysman-Colman, Eli,Studer, Armido
-
supporting information
p. 376 - 383
(2019/11/19)
-
- TEMPO-Catalyzed Aerobic Oxidative Selenium Insertion Reaction: Synthesis of 3-Selenylindole Derivatives by Multicomponent Reaction of Isocyanides, Selenium Powder, Amines, and Indoles under Transition-Metal-Free Conditions
-
A novel and efficient approach for the selenium functionalization of indoles was developed with selenium powder as the selenium source, catalyzed by 2,2,6,6-tetramethylpiperidinooxy (TEMPO) and employing O2 as the green oxidant. This protocol provides a practical route for the synthesis of 3-selenylindole derivatives and has the advantages of readily available starting materials, mild reaction conditions, and a wide scope of substrates. Electron spin-resonance (ESR) studies reveal that the approach involves the formation of nitrogen-centered radicals and selenium radicals via oxidation of in situ generated selenoates.
- Liu, Huan,Fang, Yi,Wang, Shun-Yi,Ji, Shun-Jun
-
supporting information
p. 930 - 933
(2018/02/22)
-
- Diverse catalytic reactivity of a dearomatized PN3P?-nickel hydride pincer complex towards CO2 reduction
-
A dearomatized PN3P?-nickel hydride complex has been prepared using an oxidative addition process. The first nickel-catalyzed hydrosilylation of CO2 to methanol has been achieved, with unprecedented turnover numbers. Selective methylation and formylation of amines with CO2 were demonstrated by such a PN3P?-nickel hydride complex, highlighting its versatile functions in CO2 reduction.
- Li, Huaifeng,Gon?alves, Théo P.,Zhao, Qianyi,Gong, Dirong,Lai, Zhiping,Wang, Zhixiang,Zheng, Junrong,Huang, Kuo-Wei
-
supporting information
p. 11395 - 11398
(2018/10/20)
-
- Excited-State Switching between Ligand-Centered and Charge Transfer Modulated by Metal-Carbon Bonds in Cyclopentadienyl Iridium Complexes
-
Three series of pentamethylcyclopentadienyl (Cp?) Ir(III) complexes with different bidentate ligands were synthesized and structurally characterized, [Cp?Ir(tpy)L]n+ (tpy = 2-tolylpyridinato; n = 0 or 1), [Cp?Ir(piq)L]n+ (piq = 1-phenylisoquinolinato; n = 0 or 1), and [Cp?Ir(bpy)L]m+ (bpy = 2,2′-bipyridine; m = 1 or 2), featuring a range of monodentate carbon-donor ligands within each series [L = 2,6-dimethylphenylisocyanide; 3,5-dimethylimidazol-2-ylidene (NHC); methyl)]. The spectroscopic and photophysical properties of these molecules and those of the photocatalyst [Cp?Ir(bpy)H]+ were examined to establish electronic structure-photophysical property relationships that engender productive photochemical reactivity of this hydride and its methyl analogue. The Ir(III) chromophores containing ancillary CNAr ligands exhibited features anticipated for predominantly ligand-centered (LC) excited states, and analogues bearing the NHC ancillary exhibited properties consistent with LC excited states containing a small admixture of metal-to-ligand charge-transfer (MLCT) character. However, the molecules featuring anionic and strongly σ-donating methyl or hydride ligands exhibited photophysical properties consistent with a high degree of CT character. Density functional theory calculations suggest that the lowest energy triplet states in these complexes are composed of a mixture of MLCT and ligand-to-ligand CT originating from both the Cp? and methyl or hydride ancillary ligands. The high degree of CT character in the triplet excited states of methyliridium complexes bearing C^N-cyclometalated ligands offer a striking contrast to the photophysical properties of pseudo-octahedral structures fac-Ir(C^N)3 or Ir(C^N)2(acac) that have lowest-energy triplet excited states characterized as primarily LC character with a more moderate MLCT admixture.
- Deaton, Joseph C.,Taliaferro, Chelsea M.,Pitman, Catherine L.,Czerwieniec, Rafa?,Jakubikova, Elena,Miller, Alexander J. M.,Castellano, Felix N.
-
p. 15445 - 15461
(2019/01/04)
-
- Mesoporous silica SBA-15 functionalized with acidic deep eutectic solvent: A highly active heterogeneous N-formylation catalyst under solvent-free conditions
-
Mesoporous silica SBA-15 functionalized with N-methylpyrrolidonium-zinc chloride based deep eutectic solvent (DES) is found to be a more efficient and reusable catalyst for a convenient N-formylation of a variety of amines at room temperature. N-Formylation of primary, secondary as well as heterocyclic amines have been carried out in good to excellent yields by treatment with formic acid in low loading of DES/SBA-15 an environmentally benign catalyst for the first time. The DES/SBA-15 catalyst, which possesses both Br?nsted and Lewis acidities as well as an active SBA-15 support, makes this procedure quite simple, reusable, more convenient and practical. This catalyst was tolerant of a wide range of functional groups, and it can be reused for four runs without obvious deactivation.
- Azizi, Najmedin,Edrisi, Mahtab,Abbasi, Faezeh
-
-
- Palladium-Catalyzed One-Pot Synthesis of N -Sulfonyl, N -Phosphoryl, and N -Acyl Guanidines
-
An efficient palladium-catalyzed cascade reaction of azides with isonitrile and amines is presented; it offers an alternative facile approach toward N -sulfonyl-, N -phosphoryl-, and N -acyl-functionalized guanidines in excellent yield. These series of substituted guanidines exhibit potential biological and pharmacological activities. In addition, the less reactive intermediate benzoyl carbodiimide could be isolated by silica gel column flash chromatography in moderate yield.
- Qiao, Guanyu,Zhang, Zhen,Huang, Baoliang,Zhu, Liu,Xiao, Fan,Zhang, Zhenhua
-
supporting information
p. 330 - 340
(2018/01/12)
-
- Aerobic radical-cascade cycloaddition of isocyanides, selenium and imidamides: Facile access to 1,2,4-selenadiazoles under metal-free conditions
-
A novel and facile metal-free method for the green synthesis of 1,2,4-selenadiazol-5-amine derivatives through the aerobic radical-cascade multi-component reactions of isocyanides, selenium powder and imidamides is reported herein. O2 in the air was employed as the green oxidant to achieve the cycloaddition with the generation of H2O as the sole by-product. It also features good functional group compatibility and broad substrate scope. In addition, this method was successfully applied to the functionalization of biologically active molecules.
- Fang, Yi,Zhu, Zheng-Lin,Xu, Pei,Wang, Shun-Yi,Ji, Shun-Jun
-
supporting information
p. 1613 - 1618
(2017/06/05)
-
- Cobalt(II)-Catalyzed Isocyanide Insertion Reaction with Sulfonyl Azides in Alcohols: Synthesis of Sulfonyl Isoureas
-
A Co(II)-catalyzed isocyanide insertion reaction with sulfonyl azides in alcohols to form sulfonyl isoureas via nitrene intermediate has been developed. This protocol provides a new, environmentally friendly, and simple strategy for the synthesis of sulfonyl isourea derivatives by employing a range of substrates under mild conditions.
- Jiang, Tian,Gu, Zheng-Yang,Yin, Ling,Wang, Shun-Yi,Ji, Shun-Jun
-
supporting information
p. 7913 - 7919
(2017/08/14)
-
- Facile access to a Ge(II) dication stabilized by isocyanides
-
Herein, we introduce isocyanide as a ligand in main group chemistry and describe the facile isolation of a Ge(ii) dication. The reaction of 2,6-dimethylphenylisocyanide with GeCl2 leads to the formation of a Ge(ii) dication with two [GeCl3]- molecules as counter anions. The dicationic Ge(ii) center is bound to four isocyanide ligands and also holds a lone pair of electrons. DFT calculations reveal that the dication is stabilized only by σ-donation from the four isocyanide ligands. Natural population analysis gives a charge of +0.74 on the Ge(ii) center, indicating that the positive charge is shared by the isocyanide substituents.
- Swamy,Yadav, Sandeep,Pal, Shiv,Das, Tamal,Vanka, Kumar,Sen, Sakya S.
-
supporting information
p. 7890 - 7892
(2016/07/06)
-
- Carbon Dioxide Based N-Formylation of Amines Catalyzed by Fluoride and Hydroxide Anions
-
We described herein a simple approach for N-formylation with CO2 and hydrosilane reducing agents. Fluoride and hydroxide salts efficiently catalyzed the reaction, principally through activation of the hydrosilanes, which led to hydrosilane reactivities comparable to those of NaBH4/LiAlH4. Consequently, the N-formylation of amines with CO2 could be achieved at room temperature and atmospheric pressure. The mechanism of these anionic catalysts contrasts that of the currently reported systems, for which activation of CO2 is the key mechanistic step. Using tetrabutylammonium fluoride as a simple ammonium salt catalyst, the N-formylated products of both aliphatic and aromatic amines could be obtained in excellent yields with high selectivities.
- Hulla, Martin,Bobbink, Felix D.,Das, Shoubhik,Dyson, Paul J.
-
p. 3338 - 3342
(2016/11/16)
-
- Chemoselective Schwartz Reagent Mediated Reduction of Isocyanates to Formamides
-
Addition of the in situ generated Schwartz reagent to widely available isocyanates constitutes a chemoselective, high-yielding, and versatile approach to the synthesis of variously functionalized formamides. Steric and electronic factors or the presence of sensitive functionalities (esters, nitro groups, nitriles, alkenes) do not compromise the potential of the method. Full preservation of the stereochemical information contained in the starting materials is observed. The use of formamides in the nucleophilic addition of organometallic reagents (Chida-Sato allylation, Charette-Huang addition to imidoyl triflate activated amides, Matteson homologation of boronic esters) is briefly investigated.
- Pace, Vittorio,De La Vega-Hernández, Karen,Urban, Ernst,Langer, Thierry
-
supporting information
p. 2750 - 2753
(2016/06/15)
-
- C-F Activation in Perfluorinated Arenes with Isonitriles under UV-Light Irradiation
-
Due to the great value of fluorinated arenes in agrochemistry, medicinal chemistry and materials science, development of methods for preparation of fluorinated arenes is of high importance. They can be either accessed by arene fluorination or by partial arene defluorination. However, the carbon-fluorine bond belongs to the strongest σ-bonds, which renders C-F activation highly challenging. Here it is shown that aryl and alkyl isonitriles efficiently activate the strong C-F bond in perfluoroarenes by simple UV irradiation under mild conditions. Reactions proceed by formal direct insertion of the isonitrile into the C-F bond without any transition metal. Activation occurs at arene C-F bonds whereas aliphatic C-F bonds remain unreacted. For selected perfluoroarenes C-F activation occurs with high regioselectivity and resulting imidoyl fluorides are transformed into other valuable compounds. Theoretical studies give insights into the reaction mechanism.
- Dewanji, Abhishek,Mück-Lichtenfeld, Christian,Bergander, Klaus,Daniliuc, Constantin G.,Studer, Armido
-
supporting information
p. 12295 - 12298
(2015/08/25)
-
- Acyclic aminocarbene-like palladium complex-catalyzed Suzuki-Miyaura reaction at low catalyst loadings
-
A series of air-stable aminocarbene-like palladium(II) complexes were easily prepared by the reaction of bis-aromaticisocyanide-dichloropalladium(II) with N-arylbenzamidines. 0.1 mol % of the optimal palladium complex 3a showed excellent catalytic activity for Suzuki-Miyaura cross-coupling reaction at room temperature and the desired products were isolated in up to 98% yields. Moreover, a large-scale reaction showed that 0.01 mol % 3a was enough to catalyze the coupling reaction efficiently at room temperature to give the desired product in 93% yield.
- Fang, Yi,Wang, Shun-Yi,Ji, Shun-Jun
-
supporting information
p. 9679 - 9683
(2015/12/04)
-
- N-heterocyclic carbene copper(i) catalysed N-methylation of amines using CO2
-
The N-methylation of amines using CO2 and PhSiH3 as source of CH3 was efficiently performed using a N-heterocyclic carbene copper(i) complex. The methodology was found compatible with aromatic and aliphatic primary and secondary amines. Synthetic and computational studies have been carried out to support the proposed reaction mechanism for this transformation.
- Santoro, Orlando,Lazreg, Fama,Minenkov, Yury,Cavallo, Luigi,Cazin, Catherine S. J.
-
p. 18138 - 18144
(2015/10/28)
-
- Gold-Catalyzed Reductive Transformation of Nitro Compounds Using Formic Acid: Mild, Efficient, and Versatile
-
Developing new efficient catalytic systems to convert abundant and renewable feedstocks into valuable products in a compact, flexible, and target-specific manner is of high importance in modern synthetic chemistry. Here, we describe a versatile set of mild catalytic conditions utilizing a single gold-based solid catalyst that enables the direct and additive-free preparation of four distinct and important amine derivatives (amines, formamides, benzimidazoles, and dimethlyated amines) from readily available formic acid (FA) and nitro starting materials with high level of chemoselectivity. By controlling the stoichiometry of the employed FA, which has attracted considerable interest in the area of sustainable chemistry because of its potential as an entirely renewable hydrogen carrier and as a versatile C1 source, a facile atom- and step-efficient transformation of nitro compounds can be realized in a modular fashion. Renewable formic acid as a flexible feedstock: A versatile heterogeneous gold-based catalytic system has been developed for the controlled, flexible, and target-specific reductive transformation of nitro compounds using stoichiometric equivalents of formic acid as a key starting material under mild and convenient conditions. The overall operational simplicity, high chemoselectivity, functional-group tolerance, and reusability of the catalyst make this approach an attractive and reliable tool for organic and process chemists.
- Yu, Lei,Zhang, Qi,Li, Shu-Shuang,Huang, Jun,Liu, Yong-Mei,He, He-Yong,Cao, Yong
-
p. 3029 - 3035
(2015/09/28)
-
- Comparative measure of the electronic influence of highly substituted aryl isocyanides
-
To assess the relative electronic influence of highly substituted aryl isocyanides on transition metal centers, a series of C4v-symmetric Cr(CNR)(CO)5 complexes featuring various alkyl, aryl, and m-terphenyl substituents have been prepared. A correlation between carbonyl-ligand 13C{1H} NMR chemical shift (δCO) and calculated Cotton-Kraihanzel (C-K) force constant (kCO) is presented for these complexes to determine the relative changes in isocyanide σ-donor/π-acid ratio as a function of substituent identity and pattern. For nonfluorinated aryl isocyanides possessing alkyl or aryl substitution, minimal variation in effective σ-donor/π-acid ratio is observed over the series. In addition, aryl isocyanides featuring strongly electron-releasing substituents display an electronic influence that nearly matches that of nonfluorinated alkyl isocyanides. Lower σ-donor/π-acid ratios are displayed by polyfluorinated aryl isocyanide ligands. However, the degree of this attenuation relative to nonfluorinated aryl isocyanides is not substantial and significantly higher σ-donor/π-acid ratios than CO are observed in all cases. Substituent patterns for polyfluorinated aryl isocyanides are identified that give rise to low relative σ-donor/π-acid ratios but offer synthetic convenience for coordination chemistry applications. In order to expand the range of available substitution patterns for comparison, the syntheses of the new m-terphenyl isocyanides CNArTripp2, CNp-MeArMes2, CNp-MeArDArF2, and CNp-FArDArF2 are also reported (ArTripp2 = 2,6-(2,4,6-(i-Pr)3C6H2)2C6H3); p-MeArMes2 = 2,6-(2,4,6-Me3C6H2)2-4-Me-C6H2); p-MeArDArF2 = 2,6-(3,5-(CF3)2C6H3)2-4-Me-C6H2); p-FArDArF2 = 2,6-(3,5-(CF3)2C6H3)2-4-F-C6H2).
- Carpenter, Alex E.,Mokhtarzadeh, Charles C.,Ripatti, Donald S.,Havrylyuk, Irena,Kamezawa, Ryo,Moore, Curtis E.,Rheingold, Arnold. L.,Figueroa, Joshua S.
-
p. 2936 - 2944
(2015/03/30)
-
- Palladium-catalyzed cross-coupling reaction of azides with isocyanides
-
An efficient palladium-catalyzed cross-coupling reaction of azides with isocyanides is developed, providing a general synthetic route to unsymmetric carbodiimides with excellent yields. This method shows a broad substrate scope, including not only aryl azides, but also unactivated benzyl and alkyl azides. Furthermore, from readily available substrates, Pd-catalyzed coupling with a tandem amine insertion cascade to obtain unsymmetric trisubstituted guanidines has been achieved in a one-pot fashion.
- Zhang, Zhen,Li, Zongyang,Fu, Bin,Zhang, Zhenhua
-
supporting information
p. 16312 - 16315
(2015/11/16)
-
- Isocyanide-based multicomponent reactions: Concise synthesis of spirocyclic oxindoles with molecular complexity by using a [1,5]-hydrogen shift as the key step
-
A concise multicomponent reaction of isocyanide, α-substituted allenoate, and methyleneindolinone has been disclosed. This protocol provides a fast and straightforward approach to synthesize unusual tricyclic oxindoles in an efficient and atom-economic manner. Mechanistically, the present cycloaddition may proceed through a cascade sequence involving double Michael addition, double cyclization, double [1,5]-hydrogen shift, and group migration. The introduction of a special alkyl group to the allenoate is believed to play a key role in the cascade reaction. This method also features a broad substrate scope, which is particularly useful for the delivery of a large number of compounds. Shift your perspective! An unprecedented cascade reaction, under mild conditions, involving a double Michael addition, double cyclization, and double [1,5]-hydrogen shift, followed by group migration is disclosed. This reaction offers a fast and straightforward approach to unusual polycyclic spirooxindoles (see scheme).
- Su, Shikuan,Li, Chunju,Jia, Xueshun,Li, Jian
-
supporting information
p. 5905 - 5909
(2014/05/20)
-
- Efficient isonitrile hydration through encapsulation within a hexameric self-assembled capsule and selective inhibition by a photo-controllable competitive guest
-
Catalytic hydration of neutral isonitriles to yield the corresponding N-formylamides was achieved by reversible encapsulation in a self-assembled hexameric resorcin[4]arene capsule. Encapsulation of a photochromic dithienylethene bis-cation provides different levels of competitive inhibition depending on the geometry assumed by the cationic inhibitor. The Royal Society of Chemistry 2013.
- Bianchini, Giulio,Sorella, Giorgio La,Canever, Nicolo,Scarso, Alessandro,Strukul, Giorgio
-
supporting information
p. 5322 - 5324
(2013/06/27)
-
- Efficient one-pot synthesis of unsymmetrical gold(I) N-heterocyclic carbene complexes and their use as catalysts
-
Eleven different gold(I) complexes of new NHC ligands were prepared in excellent yield, demonstrating the versatility of the new route to NHC complexes. While the influence of electronically different ligands on the synthesis of the catalysts was small, the catalytic activities of the products differed significantly.
- Hashmi, A. Stephen K.,Yu, Yang,Rominger, Frank
-
experimental part
p. 895 - 904
(2012/04/04)
-
- Multicomponent reaction to construct spirocyclic oxindoles with a Michael (triple Michael)/cyclization cascade sequence as the key step
-
Multicomponent cycloadditions with readily available isocyanides, allenoates, and isatylidene malononitriles are disclosed. This reaction, which does not require the aid of any catalyst, allows the efficient syntheses of spirocyclic oxindoles with excellent regioselectivity. Reactions with ethyl 2,3-butadienoate and various structurally diverse α- and γ-substituted allenoates are also fully explored. Remarkably, we have shown that the usual three-component process can be further developed into an unprecedented four-component cycloaddition in the presence of water, which provides a new strategy to access highly unusual tricyclic oxindoles. From a synthetic point of view, this protocol is very interesting considering the high level of complexity reached in one step. The mechanism is thought to proceed by a triple Michael/cyclization process by using allenoate as a three carbon atom component (3 C). Furthermore, multicomponent reaction with γ-substituted allenoate also results in a very interesting conversion. In such cases, the unusual cleavage of the "C=C" double bond of isatylidene malononitrile and one of the "C=C" double bonds of allenoate is always observed. Multiply your chemistry! Multicomponent reactions with readily available isocyanides, allenoates, and isatylidene malononitriles are disclosed. This protocol provides a synthetic route to an exocyclic double bond containing a spirocyclic ring in an efficient manner with excellent regioselectivity (see scheme). Copyright
- Li, Jian,Wang, Ning,Li, Chunju,Jia, Xueshun
-
supporting information; experimental part
p. 9645 - 9650
(2012/09/07)
-
- Isocyanide-based multicomponent [2+2+1]-cycloaddition strategy to construct functionalized spirocyclic oxindoles
-
Isocyanide-based three-component [2+2+1]-cycloaddition reactions from isocyanides, activated alkynes, and isatylidene malononitriles were investigated to provide a new access to spirocyclic oxindole with five-membered carbon rings. The displacement of isatylidene malononitrile with oxindolylideneacetate essentially results in opposite regioselectivity, which adds to its attractiveness. Georg Thieme Verlag Stuttgart ? New York.
- Jie, Haohua,Li, Jian,Li, Chunju,Jia, Xueshun
-
supporting information
p. 2274 - 2278
(2012/10/29)
-
- Palladium-catalyzed cascade process consisting of isocyanide insertion and benzylic C(sp3)-H activation: Concise synthesis of indole derivatives
-
Synthesis of the indole skeleton was achieved using a Pd-catalyzed cascade process consisting of isocyanide insertion and benzylic C(sp3)-H activation. It was found that slow addition of isocyanide is effective for reducing the amount of catalyst needed and Ad2PnBu is a good ligand for C(sp3)-H activation. The construction of the tetracyclic carbazole skeleton was also achieved by a Pd-catalyzed domino reaction incorporating alkyne insertion.
- Nanjo, Takeshi,Tsukano, Chihiro,Takemoto, Yoshiji
-
supporting information; experimental part
p. 4270 - 4273
(2012/10/08)
-
- 3-AMINOIMIDAZO [1,2-A] PYRIDINE DERIVATIVES AS SGLT INHIBITORS
-
Novel compounds of the formula I, in which X, Y, R, R′, R1, R1′, R1″, R2, R2′, R2″, R3, R3′, R4, R4′ and n have the meanings indicated in Patent
- -
-
Page/Page column 13
(2011/08/22)
-
- Silver hexafluoroantimonate-catalyzed three-component [2+2+1]cycloadditions of allenoates, dual activated olefins, and isocyanides
-
The intermolecular [2+2+1]multicomponent cycloadditions from readily available allenoates, dual activated olefins and isocyanides catalyzed by silver hexafluoroantimonate were studied. This protocol allowed the syntheses of highly functionalized five-membered carbocycles with exclusive regioselectivity and stereoselectivity in an efficient and atom-economical manner.
- Li, Jian,Liu, Yuejin,Li, Chunju,Jia, Xueshun
-
supporting information; experimental part
p. 913 - 917
(2011/06/18)
-
- Syntheses of spirocyclic oxindole-butenolides by using three-component cycloadditions of isocyanides, allenoates, and isatins
-
Spiro workflow! Efficient syntheses of spirocyclic oxindole-butenolides from readily available isocyanides, allenoates, and isatins are disclosed (see scheme; R1=alkyl, aryl; R2=halide, nitro, methoxy; PG=protecting group). This protocol also allows the insertion of carbon monoxide into organic molecules without the aid of a transition-metal catalyst after the hydrolysis process. Copyright
- Li, Jian,Liu, Yuejin,Li, Chunju,Jia, Xueshun
-
supporting information; experimental part
p. 7409 - 7413
(2011/08/05)
-
- A complex of gold(I) benzenethiolate with isocyanide: Synthesis and crystal and molecular structures
-
2,6-Dimethylphenyl isocyanide forms complexes with gold(I) chloride (complex 4) and gold(I) benzenethiolate (complex 5) but forms no stable complexes with gold alkanethiolates. A reaction of complex 5 with tetramethylthiuram disulfide yields gold(I) dimethyldithiocarbamate. Stable gold(III) derivatives cannot be obtained in such a way. Shortened intermolecular Au...Au contacts in complexes 4 and 5 (X-ray diffraction) suggest the presence of "aurophilic" interactions in them.
- Dyadchenko,Belov,Dyadchenko,Slovokhotov,Banaru,Lemenovskii
-
experimental part
p. 539 - 543
(2011/02/16)
-
- Synthesis, crystal structures, and reactions of 2- oxomalonylbis(arylimidoyl) chlorides and hydroxymethane tris(arylimidoyl) chlorides
-
The 2-oxomalonylbis(arylimidoyl) chlorides [C6H 3(R2-2,6)N=CC1]2CO (R = Me, 3a; Pri, 3b; H, 3c) were synthesized from C6H3(R 2-2,6)NHCHO and an excess of (COCl2/
- Bowen, Richard J.,Caddy, Judy,Coyanis, Mabel E.,Fernandes, Manuel A.,Layh, Marcus,Linganiso, Linda Z.,Maboya, Winny K.,Omondi, Bernard
-
p. 522 - 530
(2007/10/03)
-
- Convenient one-pot method for formylation of amines and alcohols using formic acid and 1,1'-oxalyldiimidazole
-
1,1'-Oxalyldiimidazole (7) reacts with formic acid (8) in acetonitrile at room temperature to give N-formylimidazole (5), which promptly undergoes aminolysis and alcoholysis to yield formamides (2) or formates (4).
- Kitagawa,Arita,Nagahata
-
p. 1655 - 1657
(2007/10/02)
-
- A Convenient and High Yielding Procedure for the Preparation of Isoselenocyanates. Synthesis and Reactivity of O-Alkylselenocarbamates.
-
A high yielding one pot procedure for the preparation of isoselenocyanate from the corresponding formamide is reported.Various aromatic and aliphatic primary amines were employed in order to prepare the isoselenocyanates to establish the generality of the procedure.O-Alkylselenocarbamates of various primary, secondary and tertiary alcohols were synthesized and their stability and comparative reactivity were studied.Radical deoxygenation of the selenocarbamate of a secondary and a tertiary alcohol was accomplished under various conditions.
- Barton, Derek H. R.,Parekh, Shyamal I.,Tajbakhsh, Mahmoud,Theodorakis, Emmanouil A.,Tse, Chi-Lam
-
p. 639 - 654
(2007/10/02)
-
- Improved procedure for N-formylation of amines to formamides using formic acid, oxalyl chloride and imidazole
-
The reaction of imidazole (15) with formyl chloride (14), generated in situ by the action of oxalyl chloride (10) on formic acid (3), afforded N-formylimidazole (7), which is a convenient formylating reagent. This procedure was used to prepare N-formyl derivatives (2) of aliphatic, aromatic and heteroaromatic amines (1) under mild conditions.
- Kitagawa,Ito,Tsutsui
-
p. 1931 - 1934
(2007/10/02)
-
- A HIGHLY EFFICIENT AND GENERAL N-MONOMETHYLATION OF FUNCTIONALIZED PRIMARY AMINES VIA FORMYLATION -- BORANE:METHYL SULFIDE REDUCTION
-
Formylation of functionalized primary aromatic and aliphatic amines with acetic formic anhydride (AFA) followed by borane:methyl sulfide reduction in the same pot affords the corresponding N-methylamines in excellent isolated yields, uncontaminated by bis alkylation; the reaction sequence is applicable to even very weakly basic and sterically hindered amines.
- Krishnamurthy, S.
-
p. 3315 - 3318
(2007/10/02)
-