- PH-Mediated Selective Synthesis of N-Allylic Alkylation or N-Alkylation Amines with Allylic Alcohols via an Iridium Catalyst in Water
-
Amination of allylic alcohols is an effective approach in the facile synthesis of N-allylic alkylation or N-alkylation amines. Recently, a series of catalysts were devised to push forward this transformation. However, current synthetic methods are typical
- Luo, Nianhua,Zhong, Yuhong,Shui, Hongling,Luo, Renshi
-
p. 15509 - 15521
(2021/11/01)
-
- FRUSTRATED LEWIS PAIR-IMPREGNATED POROUS MATERIALS AND USES THEREOF
-
Described herein are compositions composed of frustrated Lewis pairs impregnated in porous materials such as, for example, metal-organic frameworks, and their uses thereof. These compositions may allow new applications of frustrated Lewis pairs in catalysis by sequestering and protecting the frustrated Lewis pair within the nanospace of the porous material. Also provided are methods of hydrogenating an organic compound having at least one unsaturated functional group comprising using the compositions described herein.
- -
-
Page/Page column 85; 87-89
(2021/01/23)
-
- Stereoselective Construction of γ-Lactams via Copper-Catalyzed Borylacylation
-
A versatile and highly stereoselective borylative cyclization to generate polyfunctionalized γ-lactams has been developed. The stereoselective synthesis of these key ring systems is crucial due to their ubiquity in natural products. We report the diastero- and enantioselective construction of di- and trisubstituted γ-lactam cores, with examples containing an enantioenriched quaternary carbon.
- Bajohr, Jonathan,Lautens, Mark,Polishchuk, Iuliia,Torelli, Alexa,Whyte, Andrew
-
p. 7915 - 7919
(2020/11/02)
-
- Homogeneous Hydrogenation with a Cobalt/Tetraphosphine Catalyst: A Superior Hydride Donor for Polar Double Bonds and N-Heteroarenes
-
The development of catalysts based on earth abundant metals in place of noble metals is becoming a central topic of catalysis. We herein report a cobalt/tetraphosphine complex-catalyzed homogeneous hydrogenation of polar unsaturated compounds using an air- and moisture-stable and scalable precatalyst. By activation with potassium hydroxide, this cobalt system shows both high efficiency (up to 24 000 TON and 12 000 h-1 TOF) and excellent chemoselectivities with various aldehydes, ketones, imines, and even N-heteroarenes. The preference for 1,2-reduction over 1,4-reduction makes this method an efficient way to prepare allylic alcohols and amines. Meanwhile, efficient hydrogenation of the challenging N-heteroarenes is also furnished with excellent functional group tolerance. Mechanistic studies and control experiments demonstrated that a CoIH complex functions as a strong hydride donor in the catalytic cycle. Each cobalt intermediate on the catalytic cycle was characterized, and a plausible outer-sphere mechanism was proposed. Noteworthy, external inorganic base plays multiple roles in this reaction and functions in almost every step of the catalytic cycle.
- Duan, Ya-Nan,Du, Xiaoyong,Cui, Zhikai,Zeng, Yiqun,Liu, Yufeng,Yang, Tilong,Wen, Jialin,Zhang, Xumu
-
supporting information
p. 20424 - 20433
(2019/12/27)
-
- Promoting Frustrated Lewis Pairs for Heterogeneous Chemoselective Hydrogenation via the Tailored Pore Environment within Metal–Organic Frameworks
-
Frustrated Lewis pairs (FLPs) have recently been advanced as efficient metal-free catalysts for catalytic hydrogenation, but their performance in chemoselective hydrogenation, particularly in heterogeneous systems, has not yet been achieved. Herein, we demonstrate that, via tailoring the pore environment within metal–organic frameworks (MOFs), FLPs not only can be stabilized but also can develop interesting performance in the chemoselective hydrogenation of α,β-unsaturated organic compounds, which cannot be achieved with FLPs in a homogeneous system. Using hydrogen gas under moderate pressure, the FLP anchored within a MOF that features open metal sites and hydroxy groups on the pore walls can serve as a highly efficient heterogeneous catalyst to selectively reduce the imine bond in α,β-unsaturated imine substrates to afford unsaturated amine compounds.
- Niu, Zheng,Zhang, Weijie,Lan, Pui Ching,Aguila, Briana,Ma, Shengqian
-
supporting information
p. 7420 - 7424
(2019/04/27)
-
- Iron-Catalyzed Reductive Amination of Aldehydes in Isopropyl Alcohol/Water Media as Hydrogen Sources
-
Reductive amination can be carried in i-PrOH/H2O as hydrogen sources using commercially available iron carbonyl complexes. Within an aqueous alkaline environment, a hydridocarboferrate is formed and its reducing potential is exploited for hydrogenation of the imine (or iminium ion) obtained in situ from aldehydes or ketones, and primary or secondary amines in almost equimolar ratio. This completely sustainable and hydrogen-free process proceeds at 100 °C using Fe3(CO)12 as catalyst precursor under convectional heating while Fe2(CO)9 gave better results when the reaction was carried out under MW dielectric heating. Both enolizable and non-enolizable aldehydes may be successfully employed in reactions with aliphatic and aromatic amines. (Figure presented.).
- Petricci, Elena,Santillo, Niccolò,Castagnolo, Daniele,Cini, Elena,Taddei, Maurizio
-
supporting information
p. 2560 - 2565
(2018/07/29)
-
- Efficient Synthesis of Amines by Iron-Catalyzed C=N Transfer Hydrogenation and C=O Reductive Amination
-
Here we report the catalytic transfer hydrogenation (CTH) of non-activated imines promoted by a Fe-catalyst in the absence of Lewis acid co-catalysts. Use of the (cyclopentadienone)iron complex 1, which is much more active than the classical ‘Kn?lker complex’ 2, allowed to reduce a number of N-aryl and N-alkyl imines in very good yields using iPrOH as hydrogen source. The reaction proceeds with relatively low catalyst loading (0.5–2 mol%) and, remarkably, its scope includes also ketimines, whose reduction with a Fe-complex as the only catalyst has little precedents. Based on this methodology, we developed a one-pot CTH protocol for the reductive amination of aldehydes/ketones, which provides access to secondary amines in high yield without the need to isolate imine intermediates. (Figure presented.).
- Facchini, Sofia Vailati,Cettolin, Mattia,Bai, Xishan,Casamassima, Giuseppe,Pignataro, Luca,Gennari, Cesare,Piarulli, Umberto
-
p. 1054 - 1059
(2018/01/27)
-
- Palladium-catalyzed oxidative arylacetoxylation of alkenes: Synthesis of indole and indoline derivatives
-
A method for the oxidative arylacetoxylation of alkenes has been developed to synthesize indole and indoline derivatives from readily accessible substrates. The cinnamyl tethered anilines with picolinamide as a directing group provided 3-substituted indoles via intramolecular oxidative arylacetoxylation, and the 2-methyl substituted cinnamyl anilines furnished indoline derivatives with 3-position quaternary stereocenters in good to excellent yields via sequential intramolecular oxidative arylacetoxylation, hydrolysis and oxidation steps.
- Karnakanti, Shuklachary,Zang, Zhong-Lin,Zhao, Sheng,Shao, Pan-Lin,Hu, Ping,He, Yun
-
supporting information
p. 11205 - 11208
(2017/10/17)
-
- Iron-Catalyzed Allylic Amination Directly from Allylic Alcohols
-
Allylic amination, directly from alcohols, has been demonstrated without any Lewis acid activators using an efficient and regiospecific molecular iron catalyst. Various amines and alcohols were employed and the reaction proceeded through the oxidation/reduction (redox) pathway. A direct one-step synthesis of common drugs, such as cinnarizine and nafetifine, was exhibited from cinnamyl alcohol that produced water as side product. The iron way! A direct amination of allylic alcohols has been demonstrated without the need of Lewis acid activators using an efficient and regiospecific molecular iron catalyst. A range of amines and alcohols were tolerated, and the reaction was found to procced through an oxidation/reduction (redox) pathway (see scheme).
- Emayavaramban, Balakumar,Roy, Moumita,Sundararaju, Basker
-
p. 3952 - 3955
(2016/03/16)
-
- Exclusive chemoselective reduction of imines in the coexistence of aldehydes using AuNPore catalyst
-
Aldimines (R1HC=NR2) were reduced in the coexistence of aldehydes (R1CHO) with 100% chemoselectivity by the use of AuNPore giving corresponding amines (R1H2C-NHR2) in high chemical yields.
- Takale, Balaram S.,Tao, Shan Mou,Yu, Xiao Qiang,Feng, Xiu Juan,Jin, Tienan,Bao, Ming,Yamamoto, Yoshinori
-
supporting information
p. 2558 - 2561
(2014/05/20)
-
- Palladium catalyzed intermolecular hydroamination of 1-substituted allenes: An atom-economical method for the synthesis of N-allylamines
-
The palladium complex [(3IPtBu)Pd(allyl)]OTf previously displayed excellent catalytic activity for the hydroamination of 1,1-dimethylallene with anilines, selectively producing the branched substituted allylamine product (kinetic product) in high conversion. In the current report, the scope of this hydroamination reaction has been expanded to include both alkyl amines and anilines in combination with an array of seven alkyl and aryl allenes. For the majority of amines investigated, the hydroamination of 1,1-dimethylallene, cyclohexylallene, benzylallene, and select aryl allenes with alkyl amines gave the branched substituted allylamine product in nearly quantitative conversion at ambient temperature in less than 1 hour. In contrast, anilines displayed a more limited reaction scope and yielded the linear hydroamination product (thermodynamic product) with all allenes other than 1,1-dimethylallene. Both branched and linear products could be formed selectively in the hydroamination of p-fluorophenylallene with alkyl amines through careful control of [(3IPtBu)Pd(allyl)]OTf catalyst loading and reaction duration. Overall, the branched allylamines produced are useful synthetic intermediates due to their available unsaturated vinyl group, while the linear allylamine products are chemically similar to a class of known pharmaceuticals. The Royal Society of Chemistry 2013.
- Beck, John F.,Samblanet, Danielle C.,Schmidt, Joseph A. R.
-
p. 20708 - 20718
(2013/11/06)
-
- Catalyst-free alkylation of aromatic amines with aldehydes
-
In the absence of any additional catalysts, a series of aromatic amines were alkylated with a range of aromatic and aliphatic aldehydes. Moderate to excellent isolated yields (up to 94%) were obtained under mild conditions. Simultaneously, the reaction ti
- He, Qi,Wang, Zhouyu,Qian, Shan,Jiang, Zhenju,Li, Jianhui,Jiang, Dehong,Ai, Wensi
-
p. 369 - 373
(2013/07/26)
-
- Transfer hydrogenation of imines with carboxyl-tailed benzothiazoline as readily removable hydrogen donor
-
A benzothiazoline bearing 4-carboxyphenyl group at 2-position was developed as an efficient hydrogen donor for the transfer hydrogenation reaction. Introduction of the carboxyl group significantly facilitated the removal of the residual benzothiazoline an
- Zhu, Chen,Akiyama, Takahiko
-
supporting information; experimental part
p. 416 - 418
(2012/02/05)
-
- Palladium-catalyzed amination of allyl alcohols
-
An efficient catalytic amination of aryl-substituted allylic alcohols has been developed. The complex [(η3-allyl)PdCl]2 modified by a bis phosphine ligand, L, has been used as catalyst in the reaction that afforded a wide range of allyl amines in good to excellent yield under mild conditions.
- Ghosh, Raju,Sarkar, Amitabha
-
experimental part
p. 8508 - 8512
(2011/12/04)
-
- Regio- and enantioselective allylic substitution with less active N- or O-nucleophiles catalyzed by iridium-complex of bis(oxazolinyl)pyridine
-
The utility of hydroxylamines as nitrogen nucleophiles was investigated in the iridium-catalyzed regio- and enantioselective allylic substitution. Allylic substitution with hydroxylamines proceeded with good enantioselectivities by using the iridium-complex of bis(oxazolinyl)pyridine ligand. The good regio- and enantioselectivities were also achieved in the reaction with alkylamines, p-anisidine, and 4-methoxyphenol.
- Miyabe, Hideto,Moriyama, Katsuhiko,Takemoto, Yoshiji
-
experimental part
p. 714 - 720
(2011/07/29)
-
- Br?nsted acid catalyzed reductive amination with benzothiazoline as a highly efficient hydrogen donor
-
Reductive amination of aldehyde and amine proceeded smoothly in the presence of benzothiazoline as efficient hydrogen source by means of 20 mol% trifluoroacetic acid to give the corresponding amines in excellent yields. Hydrogen-donor abilities of benzothiazoline, benzimidazoline, and benzoxazoline were compared. Georg Thieme Verlag Stuttgart - New York.
- Zhu, Chen,Akiyama, Takahiko
-
supporting information; experimental part
p. 1251 - 1254
(2011/06/28)
-
- Pd(OAc)2/dppf as an efficient and highly active catalyst for the allylation of amines, alcohols and carboxylic acids with 1-phenyl-1-propyne
-
Pd(OAc)2/1,1′-bis(diphenylphosphino)ferrocene as an efficient, highly active catalyst for the allylation of amines, alcohols and carboxylic acids with 1-phenyl-1-propyne has been developed. The effect of various reaction parameters, such as ligand, time, solvent, temperature, metal: ligand ratio and catalyst concentration on yields of the product were investigated. The optimized procedure works well under mild operating conditions and permits rapid generation of a library for various allylated products.
- Wagh, Yogesh S.,Sawant, Dinesh N.,Tambade, Pawan J.,Dhake, Kishor P.,Bhanage, Bhalchandra M.
-
experimental part
p. 2414 - 2421
(2011/04/26)
-
- A versatile catalyst for reductive animation by transfer hydrogenation
-
An iridium catalyst enables the reductive amination of carbonyl groups with unprecedented substrate scope, selectivity, and activity using formic acid as the hydrogen source (see scheme) The catalyst system provides significant improvement over commonly used boron hydrides.
- Wang, Chao,Pettman, Alan,Basca, John,Xiao, Jianliang
-
supporting information; experimental part
p. 7548 - 7552
(2010/12/19)
-
- Allylic amination of internal alkynes with aromatic and aliphatic amines using polymer-supported triphenylphosphane-palladium complex as a heterogeneous and recyclable catalyst
-
A facile and novel protocol for the allylic amination of internal alkynes with amines by using a polymer-supported triphenylphosphane-palladium complex [PS-TPP-Pd] as a highly active heterogeneous reusable catalyst was developed. The catalyst exhibited remarkable activity and is re-usable over five consecutive cycles. The protocol was applicable for a variety of hindered and functionalized aromatic/ aliphatic amines and afforded the desired allylic products in good to excellent yield.
- Wagh, Yogesh S.,Tambade, Pawan J.,Sawant, Dinesh N.,Bhanage, Bhalchandra M.
-
experimental part
p. 5071 - 5076
(2010/10/21)
-
- Platinum-catalyzed direct amination of allylic alcohols under mild conditions: Ligand and microwave effects, substrate scope, and mechanistic study
-
Transition metal-catalyzed amination of allylic compounds via a π-allylmetal intermediate is a powerful and useful method for synthesizing allylamines. Direct catalytic substitution of allylic alcohols, which forms water as the sole coproduct, has recently attracted attention for its environmental and economical advantages. Here, we describe the development of a versatile direct catalytic amination of both aryl- and alkyl-substituted allylic alcohols with various amines using Pt-Xantphos and Pt-DPEphos catalyst systems, which allows for the selective synthesis of various monoallylamines, such as the biologically active compounds Naftifine and Flunarizine, in good to high yield without need for an activator. The choice of the ligand was crucial toward achieving high catalytic activity, and we demonstrated that not only the large bite-angle but also the linker oxygen atom of the Xantphos and DPEphos ligands was highly important. In addition, microwave heating dramatically affected the catalyst activity and considerably decreased the reaction time compared with conventional heating. Furthermore, several mechanistic investigations, including 1H and 31P{1H} NMR studies; isolation and characterization of several catalytic intermediates, Pt(xantphos)Cl2, Pt(η2-C3H5OH)(xantphos), etc; confirmation of the structure of [Pt(η3-allyl)(xantphos)]OTf by X-ray crystallographic analysis; and crossover experiments, suggested that formation of the π-allylplatinum complex through the elimination of water is an irreversible rate-determining step and that the other processes in the catalytic cycle are reversible, even at room temperature.
- Ohshima, Takashi,Miyamoto, Yoshiki,Ipposhi, Junji,Nakahara, Yasuhito,Utsunomiya, Masaru,Mashima, Kazushi
-
body text
p. 14317 - 14328
(2010/02/16)
-
- Allylation of N-Heterocycles with allylic alcohols employing self-assembling palladium phosphane catalysts
-
The first palladium catalyst system that allows the direct allylation of indoles with allylic alcohols as substrates with water being the only byproduct is presented. The application of self-assembing ligands based on complementary hydrogen bonding was the key to success.
- Usui, Ippei,Schmidt, Stefan,Keller, Manfred,Breit, Bernhard
-
scheme or table
p. 1207 - 1210
(2009/04/06)
-