- Pyrimidopteridine-Catalyzed Hydroamination of Stilbenes with Primary Amines: A Dual Photoredox and Hydrogen Atom Transfer Catalyst
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The applicability of a heteroaromatic photoredox catalyst in an additive-free photo-mediated hydroamination of stilbenes is described. Initiated by the excitation of a highly potent organic pyrimidopteridine photoredox catalyst (E?[PrPPT?/PrPPT·-] = +2.10 V vs SCE in MeCN), the photo-mediated hydroamination of stilbenes was enabled using unprotected, primary aliphatic, allylic, benzylic amines for the synthesis of various α-phenyl phenethylamine derivatives. Notably, the stereogenic center of α-chiral amines was fully preserved. Both starting materials serve as competent quenching partners. Fluorescence- and competitive fluorescence-quenching experiments as well as electron paramagnetic resonance spectroscopic analysis and density functional theory calculations allowed a plausible reaction mechanism to be deduced.
- Taeufer, Tobias,Hauptmann, Richy,El-Hage, Firas,Mayer, Thea S.,Jiao, Haijun,Rabeah, Jabor,Pospech, Jola
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p. 4862 - 4869
(2021/05/04)
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- Direct Access to Primary Amines from Alkenes by Selective Metal-Free Hydroamination
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Direct and selective synthesis of primary amines from easily available precursors is attractive yet challenging. Herein, we report the rapid synthesis of primary amines from alkenes via metal-free regioselective hydroamination at room temperature. Ammonium carbonate was used as ammonia surrogate for the first time, allowing for efficient conversion of terminal and internal alkenes into linear, α-branched, and α-tertiary primary amines under mild conditions. This method provides a straightforward and powerful approach to a wide spectrum of advanced, highly functionalized primary amines which are of particular interest in pharmaceutical chemistry and other areas.
- Du, Yi-Dan,Chen, Bi-Hong,Shu, Wei
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supporting information
p. 9875 - 9880
(2021/03/29)
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- Air Stable Iridium Catalysts for Direct Reductive Amination of Ketones
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Half-sandwich iridium complexes bearing bidentate urea-phosphorus ligands were found to catalyze the direct reductive amination of aromatic and aliphatic ketones under mild conditions at 0.5 mol % loading with high selectivity towards primary amines. One of the complexes was found to be active in both the Leuckart–Wallach (NH4CO2H) type reaction as well as in the hydrogenative (H2/NH4AcO) reductive amination. The protocol with ammonium formate does not require an inert atmosphere, dry solvents, as well as additives and in contrast to previous reports takes place in hexafluoroisopropanol (HFIP) instead of methanol. Applying NH4CO2D or D2 resulted in a high degree of deuterium incorporation into the primary amine α-position.
- Polishchuk, Iuliia,Sklyaruk, Jan,Lebedev, Yury,Rueping, Magnus
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supporting information
p. 5919 - 5922
(2021/03/08)
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- Ultra-small cobalt nanoparticles from molecularly-defined Co-salen complexes for catalytic synthesis of amines
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We report the synthesis of in situ generated cobalt nanoparticles from molecularly defined complexes as efficient and selective catalysts for reductive amination reactions. In the presence of ammonia and hydrogen, cobalt-salen complexes such as cobalt(ii)-N,N′-bis(salicylidene)-1,2-phenylenediamine produce ultra-small (2-4 nm) cobalt-nanoparticles embedded in a carbon-nitrogen framework. The resulting materials constitute stable, reusable and magnetically separable catalysts, which enable the synthesis of linear and branched benzylic, heterocyclic and aliphatic primary amines from carbonyl compounds and ammonia. The isolated nanoparticles also represent excellent catalysts for the synthesis of primary, secondary as well as tertiary amines including biologically relevant N-methyl amines.
- Beller, Matthias,Chandrashekhar, Vishwas G.,Gawande, Manoj B.,Jagadeesh, Rajenahally V.,Kalevaru, Narayana V.,Kamer, Paul C. J.,Senthamarai, Thirusangumurugan,Zbo?il, Radek
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p. 2973 - 2981
(2020/03/27)
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- Alkaline-metal-catalyzed one-pot aminobenzylation of aldehydes with toluenes
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A novel and easily accessible MN(SiMe3)2 (M = Li or Na)/Cs2CO3 co-catalyzed benzylation of in situ generated N-(trimethylsilyl) aldimines with toluene derivatives has been successfully developed. The catalyst exhibits high chemoselectivity for deprotonation of toluenes at the benzylic position. The utility of this system is exemplified by the one-pot synthesis of a diverse array of bioactive 1,2-diarylethylamines with excellent efficiency and broad functional group tolerance.
- Liu, Guoqing,Walsh, Patrick J.,Mao, Jianyou
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supporting information
p. 8514 - 8518
(2019/10/11)
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- Catalytic Direct-Type Addition Reactions of Alkylarenes with Imines and Alkenes
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Catalytic addition reactions of very weakly acidic nonactivated alkylarenes such as toluene and its derivatives were developed by using a strongly basic mixed catalyst system under mild reaction conditions. The addition reactions with imines and alkenes proceeded smoothly under proton-transfer conditions to afford the desired products in good to high yields, and high levels of regio- and stereoselectivity were achieved. It was also revealed that the asymmetric addition reaction of an alkylarene was possible.
- Yamashita, Yasuhiro,Suzuki, Hirotsugu,Sato, Io,Hirata, Tsubasa,Kobayashi, Shū
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supporting information
p. 6896 - 6900
(2018/05/14)
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- Hydrogen bond directed aerobic oxidation of amines via photoredox catalysis
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An application of H-bonding interactions for directing the α-C-H oxidation of amines to amides and amino-ketones catalyzed by an organic photocatalyst is reported. The high efficiency of this method is demonstrated by the aerobic oxidation of pyrrolidines, diarylamines and benzylamines bearing urea groups with high yields and a wide substrate scope.
- Wang, Hongyu,Man, Yunquan,Wang, Kaiye,Wan, Xiuyan,Tong, Lili,Li, Na,Tang, Bo
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supporting information
p. 10989 - 10992
(2018/10/08)
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- APPLICATIONS OF N6-SUBSTITUTED ADENOSINE DERIVATIVE AND N6-SUBSTITUTED ADENINE DERIVATIVE TO CALMING, HYPNOSES, CONVULSION RESISTANCE, EPILEPTIC RESISTANCE, PARKINSON DISEASE RESISTANCE, AND DEMENTIA PREVENTION AND TREATMENT
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PROBLEM TO BE SOLVED: To prepare analgesics, hypnotic agents, anticonvulsant agents, antiepileptics, antiparkinson drugs, dementia prophylactics, and health care food. SOLUTION: The present invention relates to an N6-substituted adenosine derivative and an N6-substituted adenine derivative selected from the group consisting of specific compounds. The present invention also relates to a pharmaceutical composition at least comprising a therapeutically effective amount of the compounds and a pharmaceutically acceptable carrier. The invention further relates to the compounds used in preparation of analgesics, hypnotic agents, anticonvulsant agents, antiepileptics, antiparkinson drugs, dementia prophylactics, and health care food. COPYRIGHT: (C)2016,JPO&INPIT
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Paragraph 0186
(2018/10/27)
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- An efficient synthesis of substituted isoxazolopyrroloisoquinolines via diastereoselective N-acyliminium ion cyclization
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A simple and efficient strategy was developed for the synthesis of fused pyrrolo[2,1-a]isoquinoline ring systems. The 5- and 6-substituted isoxazolopyrroloisoquinolines were readily prepared via diastereoselective N-acyliminium ion cyclization of 5-(1-R(or 2-R)-substituted-2-phenylethyl)-6-hydroxytetrahydro-4H-pyrrolo[3,4-d]isoxazol-4-ones derived from the corresponding bicyclic dihydroisoxazoles.
- Ledovskaya, Maria S.,Molchanov, Alexander P.,Boitsov, Vitaly M.,Kostikov, Rafael R.,Stepakov, Alexander V.
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p. 1952 - 1958
(2015/04/14)
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- Rapid, one-pot synthesis of α,α-disubstituted primary amines by the addition of Grignard reagents to nitriles under microwave heating conditions
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A series of α,α-disubstituted amines have been prepared in a simple and efficient one-pot procedure by the addition of Grignard reagents to a series of aliphatic, aromatic, and heteroaromatic nitriles. Key to this reported procedure is the unprecedented addition of the Grignard reagent to the nitrile under heating by microwave irradiation which both significantly improves reaction yields and reduces reaction times. In general, the Grignard addition reaction is complete within 5-10 min at 100 °C followed by rapid reduction with sodium borohydride to give the target amines.
- Gregg, Brian T.,Golden, Kathryn C.,Quinn, John F.,Wang, Hong-Jun,Zhang, Wei,Wang, Ruifang,Wekesa, Francis,Tymoshenko, Dmytro O.
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experimental part
p. 3978 - 3981
(2009/10/04)
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- Carbon-carbon bond formations at the benzylic positions of N-benzylxanthone imines and N-benzyldi-1-naphthyl ketone imine
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Two N-benzyl imines are designed to allow for carbon-carbon bond formations at the aminated benzylic positions. Direct benzylic arylation reactions of N-benzylxanthone imine with aryl chlorides proceed under palladium catalysis in the presence of cesium hydroxide, yielding the corresponding benzhydrylamine derivatives. Alkylation reactions of N-benzyldi-1-naphthyl ketone imine with alkyl halides in the presence of potassium tert-butoxide afford the corresponding 1-phenylalkylamines in high yields. Conjugate addition of N-benzyldi-1-naphthyl ketone imine is also described.
- Niwa, Takashi,Suehiro, Takafumi,Yorimitsu, Hideki,Oshima, Koichiro
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experimental part
p. 5125 - 5131
(2009/11/30)
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- Deprotection of a primary Boc group under basic conditions
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Treatment of a primary t-butyl carbamate (Boc) group with excess sodium t-butoxide in slightly wet tetrahydrofuran or 2-methyltetrahydrofuran provides the corresponding primary amine in excellent yield. We believe the reaction proceeds through an isocyanate intermediate.
- Tom, Norma J.,Simon, Wendy M.,Frost, Heather N.,Ewing, Marcus
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p. 905 - 906
(2007/10/03)
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- Process for producing optically active 3,3,3-Trifluoro-2-Hydroxy-2-Methylpropionic acid, and salt thereof
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There are disclosed are a diastereomer salt of formula (1): a process for producing the same, a process for producing optically active 3,3,3-trifluoro-2-hydroxy-2-methylpropionic acid of formula (2′): a novel optically active amine compound of formula (4): a novel optically active amine compound of formula (8): an imine compound of formula (7) or (11):
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- BMS-196085: A potent and selective full agonist of the human β3 adrenergic receptor
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A series of 4-hydroxy-3-methylsulfonanilido-1,2-diarylethylamines were prepared and evaluated for their human β3 adrenergic receptor agonist activity. SAR studies led to the identification of BMS-196085 (25), a potent β3 full agonist (Ki=21 nM, 95% activation) with partial agonist (45%) activity at the β1 receptor. Based on its desirable in vitro and in vivo properties, BMS-196085 was chosen for clinical evaluation.
- Gavai,Sher,Mikkilineni,Poss,McCann,Girotra,Fisher,Wu,Bednarz,Mathur,Wang,Sun,Slusarchyk,Skwish,Allen,Hillyer,Frohlich,Abboa-Offei,Cap,Waldron,George,Tesfamariam,Harper,Ciosek Jr.,Young,Dickinson,Seymour,Arbeeny,Washburn
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p. 3041 - 3044
(2007/10/03)
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- Synthesis and structure-activity relationships of potential anticonvulsants based on 2-piperidinecarboxylic acid and related pharmacophores
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Using N-(2,6-dimethyl)phenyl-2-piperidinecarboxamide (1) and N-(α-methylbenzyl)-2-piperidinecarboxamide (2) as structural leads, a variety of analogues were synthesised and evaluated for anticonvulsant activity in the MES test in mice. In the N-benzyl series, introduction of 3-Cl, 4-Cl, 3,4-Cl2, or 3-CF3 groups on the aromatic ring led to an increase in MES activity. Replacement of the α-methyl group by either i-Pr or benzyl groups enhanced MES activity with no increase in neurotoxicity. Substitution on the piperidine ring nitrogen led to a decrease in MES activity and neurotoxicity, while reduction of the amide carbonyl led to a complete loss of activity. Movement of the carboxamide group to either the 3- or 4-positions of the piperidine ring decreased MES activity and neurotoxicity. Incorporation of the piperidine ring into a tetrahydroisoquinoline or diazahydrinone nucleus led to increased neurotoxicity. In the N-(2,6-dimethyl)phenyl series, opening of the piperidine ring between the 1- and 6-positions gave the active norleucine derivative 75 (ED50 = 5.8 mg kg-1, TD50 = 36.4 mg kg-1, PI = 6.3). Replacement of the piperidine ring of 1 by cycloalkane (cyclohexane, cyclopentane, and cyclobutane) resulted in compounds with decreased MES activity and neurotoxicity, whereas replacement of the piperidine ring by a 4-pyridyl group led to a retention of MES activity with a comparable PI. Simplification of the 2-piperidinecarboxamide nucleus of 1 into a glycinecarboxamide nucleus led to about a six-fold decrease in MES activity. The 2,6-dimethylanilides were the most potent compounds in the MES test in each group of compounds evaluated, and compounds 50 and 75 should be useful leads in the development of agents for the treatment of tonic-clonic and partial seizures in man.
- Ho, Bin,Michael Crider,Stables, James P
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p. 265 - 286
(2007/10/03)
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- An ammonia equivalent for the dimethyltitanocene-catalyzed intermolecular hydroamination of alkynes
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(Equation presented) Commercially available α-aminodiphenylmethane 1 (benzhydrylamine) serves as a convenient ammonia equivalent in the dimethyltitanocene-catalyzed intermolecular hydroamination of alkynes. The primary formed imines can be hydrogenated and cleaved directly to the corresponding primary amines by catalytic hydrogenation using Pd/C as catalyst.
- Haak, Edgar,Siebeneicher, Holger,Doye, Sven
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p. 1935 - 1937
(2007/10/03)
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- Lithium perchlorate mediated three component reaction for the preparation of primary amines
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In the presence of lithium perchlorate in diethyl ether, LPDE, a three- component reaction between aldehydes, sodium hexamethyldisilazane or lithium hexamethyldisilazane, LHMDS, and different nucleophiles proceeds smoothly to afford primary amines in good yields.
- Saidi, Mohammad R.,Javanshir, Shahrzad,Mojtahedi, Mohammad M.
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p. 330 - 331
(2007/10/03)
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- Convenient Access to Primary Amines by Employing the Barbier-Type Reaction of N-(Trimethylsilyl)imines Derived from Aromatic and Aliphatic Aldehydes
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A new versatile preparation of primary amines via benzylation of aromatic and aliphatic aldimines is described. Sonochemical and traditional methods for generation of the reactive intermediates are compared and contrasted. Competitive reactions were analyzed via free energy relationships to support the proposed alkylative mechanism.
- Gyenes, Ferenc,Bergmann, Kathryn E.,Welch, John T.
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p. 2824 - 2828
(2007/10/03)
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- Arylalkyl-amines and -amides having anticonvulsant and neuroprotective properties
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There is provided a method of treatment of neurological disorders, such as epilepsy, stroke and cerebral ischaemia, which comprises the administration of a compound of Formula I: STR1 wherein, Ar1 and Ar2, which may be the same or different, independently represent phenyl or phenyl substituted by one or more of amino, nitro, halogen, hydroxy, C1 to 6 alkoxy, C1 to 6 alkyl or cyano; R1 represents hydrogen, C1 to 6 alkyl, C1 to 6 alkoxycarbonyl; R2 represents hydrogen or COCH2 NH2 ; R3 represents hydrogen or C1 to 6 alkyl; in addition, when R2 represents hydrogen either one or both of Ar1 and Ar2 may also represent 2-, 3- or 4-pyridinyl and R1 may also represent trihalomethyl; or a pharmaceutically acceptable salt thereof. Some of the compounds of formula I are novel, and these are also provided, together with pharmaceutical compositions containing the novel compounds.
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- Regiochemistry on Photoamination of Stilbene Derivatives with Ammonia via Electron Transfer
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The regiochemistry of photoamination of 1,2-diarylethene (1) with ammonia in the presence of p-dicyanobenzene (DCNB) has been investigated.The photoamination of stilbene and p,p'-dimethoxystilbene gave 1-amino-1,2-diphenylethane and 1-amino-1,2-bis(p-methoxyphenyl)ethane, respectively.The photoamination of unsymmetric 1-aryl-2-phenylethene having an alkoxy group on the para position occurred selectively to give 1-amino-2-aryl-1-phenylethane.On the other hand, the photoamination of 1-aryl-2-phenylethene having a methyl and chloro group on the para position or methoxy group on the meta and ortho positions gave both 1-amino-2-aryl-1-phenylethane and 1-amino-1-aryl-2-phenylethane.The regiochemistry is related with the distribution of positive charge in the cation radicals of 1 generated from photochemical electron transfer to DCNB.
- Yasuda, Masahide,Isami, Toshihiro,Kubo, Jun-ichi,Mizutani, Manabu,Yamashita, Toshiaki,et al.
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p. 1351 - 1354
(2007/10/02)
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- Synthesis of α,α-Disubstituted α-Amino Acid Amides by Phase-Transfer Catalyzed Alkylation
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α,α-Disubstituted α-amino acid amides were prepared in 17-88 percent chemical yield by the phase-transfer catalyzed alkylation of N-benzylidene α-H amino acid amides, followed by weak acidic hydrolysis of the Schiff bases.
- Kaptein, Bernard,Boesten, Wilhelmus H. J.,Broxterman, Quirinus B.,Schoemaker, Hans E.,Kamphuis, Johan
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p. 6007 - 6010
(2007/10/02)
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- PCP receptor ligands and the use thereof
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The invention relates to methods for the treatment or prevention of neuronal loss in ischemia, hypoxia, hypoglycemia, brain and spinal cord trauma as well as for treatment of Alzheimer''s disease, amyotrophic lateral sclerosis, Huntington''s disease, and Down''s Syndrome by administering a pharmaceutical composition comprising an effective amount of 10,5-(iminomethano)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (IDDC) or derivatives thereof to an animal.
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- SOME ORGANIC REACTIONS PROMOTED BY SAMARIUM DIIODIDE
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Various homoallylic alcohols and homobenzylic alcohols were prepared by the reaction between aldehydes and allylic or benzylic halides in the presence of samarium diiodide.This iodide is also a very good reagent for formation of pinacols from aldehydes or ketones.The reactions are especially fast and selective in the case of substituted benzaldehydes.The reactivities of various nitrogen functional groups (imine, oxime, nitro, azo, cyano) towards SmI2 were also examined.
- Souppe, J.,Danon, L.,Namy, J.L.,Kagan, H.B.
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p. 227 - 236
(2007/10/02)
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- STEREOCHEMICAL INVESTIGATIONS. LI. STEREOCHEMICAL INVESTIGATION OF DERIVATIVES OF (-)-1,2-DIPHENYLETHYLAMINE
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Optically active 1,2-diphenylethylamine was obtained, its optical purity was determined, and its configuration was confirmed by the circular dichroism (CD) method.
- Potapov, V. M.,Dem'yanovich, V. M.,Solov'eva, L. D.,Vendrova, O. P.
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p. 683 - 686
(2007/10/02)
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- Metalated Nitrogen Derivatives of Carbonic Acid in Organic Synthesis, XV. - 2-Azaallyl Anions from Dialkyl N-(Benzyl)imidodithiocarbonates, -monothiocarbonates, and -carbonates as α-Benzylamine Anion Equivalents
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S,S'-Dimethyl N-(benzyl)imidodithiocarbonate (4a) was deprotonated by means of potassium tert-butoxide in THF or butyllithium in THF/HMPTA/hexane to give the 2-azaallyl anion 7a.Its alkylation yields mixtures of the α- and γ-substitution products 11a and 14a.In contrast, anion 7b, obtained from the S,S'-diethyl derivative 4b, is trapped by electrophiles predominantly in α-position, yielding 11b with high regioselectivity.Thus 4b constitutes a synthetic equivalent for α-metalated benzylamine 1.The less acidic O,O'-and O,S-dialkyl derivatives 5 or 6 were also dep rotonated and alkylated to give only α-adducts 12 or 13 via anions 8 or 9. - Lithium diisopropylamide under kinetic control predominantly abstracts a proton from an S-methyl group of 4a.The intermediate lithium compound 21 was trapped as silane 23 (besides 14aa). - Some further deprotonation experiments were also performed with the imino compounds 11aa, 11ab, 32a, and 32b in order to explore the scope of the metalation reaction.
- Hoppe, Dieter,Beckmann, Ludger
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p. 1751 - 1764
(2007/10/02)
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- N-benzyl-2,2-dimethoxy-acetamides
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N-benzyl-2,2-dimethoxy-acetamides having the formula STR1 and processes for preparing the same. These acetamides are useful for the production of 2H-3-isoquinolones by acid cyclization and said 2H-3-isoquinolones are in turn useful as starting materials inter alia in the synthesis of 1,4-dihydro-1,4-etheno-isoquinolin-3(2H)ones, which are valuable chemotherapeutic agents as disclosed in U.S. Pat. No. 3,781,436.
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