- Catalyst-Free Visible-Light-Mediated Iodoamination of Olefins and Synthetic Applications
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Herein we report a catalyst- and metal-free visible-light-mediated protocol enabling the iodoamination of miscellaneous olefins. This protocol is characterized by high yields under environmentally benign reaction conditions utilizing commercially available substrates and a green and biodegradable solvent. Furthermore, the protocol allows for late-stage functionalization of bioactive molecules and can be scaled to gram quantities of product, which offers manifold possibilities for further transformations, including morpholine, piperidine, pyrrolidine, and aziridine synthesis.
- Engl, Sebastian,Reiser, Oliver
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supporting information
p. 5581 - 5586
(2021/07/26)
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- 5-Aryloxazolidines as Reagents for Double Alkylation of Arenes: A Novel Synthesis of 4-Aryltetrahydroisoquinolines
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5-Aryloxazolidines react with arenes under Lewis or Br?nsted acid conditions via the Friedel-Crafts/Pictet-Spengler double alkylation sequence to give alkaloid-like 4-aryltetrahydroisoquinolines in 12-94% yields. Three approaches for the controlled insertion of substituents into the target molecules and application of oxazolidine derivatives such as 1-arylethanol-2-amines or 4-hydroxytetrahydroisoquinolines in the alkylation of arenes are also described. An unprecedented two-step easily scalable synthesis of the 4-aryltetrahydroisoquinoline core from aromatic aldehyde was achieved applying oxazolidine methodology.
- Buev, Evgeny M.,Moshkin, Vladimir S.,Smorodina, Anastasia A.,Sosnovskikh, Vyacheslav Y.
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p. 15307 - 15317
(2021/10/20)
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- Design and Scalable Synthesis of N-Alkylhydroxylamine Reagents for the Direct Iron-Catalyzed Installation of Medicinally Relevant Amines**
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Secondary and tertiary alkylamines are privileged substance classes that are often found in pharmaceuticals and other biologically active small molecules. Herein, we report their direct synthesis from alkenes through an aminative difunctionalization reaction enabled by iron catalysis. A family of ten novel hydroxylamine-derived aminating reagents were designed for the installation of several medicinally relevant amine groups, such as methylamine, morpholine and piperazine, through the aminochlorination of alkenes. The method has excellent functional group tolerance and a broad scope of alkenes was converted to the corresponding products, including several drug-like molecules. Besides aminochlorination, the installation of other functionalities through aminoazidation, aminohydroxylation and even intramolecular carboamination reactions, was demonstrated, further highlighting the broad potential of these new reagents for the discovery of novel amination reactions.
- Delcaillau, Tristan,Falk, Eric,Gürtler, Laura,Makai, Szabolcs,Morandi, Bill
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supporting information
p. 21064 - 21071
(2020/09/21)
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- Method for synthesizing N-methylphenethyl ethanolamine and hydrochloride thereof
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The invention relates to a method for synthesizing N-methylphenethyl ethanolamine and hydrochloride thereof, and belongs to the technical field of organic synthesis. The method comprises the following steps: dissolving styrene and sodium chloride in a mixed solvent, sequentially adding sulfuric acid aqueous solution and sodium periodate at negative 5-5 DEG C, heating and stirring to react, adding a sodium thiosulfate aqueous solution for a quenching reaction, regulating the pH value to be 8, extracting and concentrating to obtain intermediate (I); adding a methylamine aqueous solution into a reaction bottle, slowly dropwise adding the intermediate (I) into the reaction bottle, stirring overnight at room temperature, performing HPLC detection reaction, and concentrating at reduced pressure to obtain the N-methylphenethyl ethanolamine. In the method for synthesizing N-methylphenethyl ethanolamine, raw materials have low price and are easily available, a low-price conventional reagent is adopted as the reagent, so that the method has low synthesizing cost, mild reaction condition and high conversion rate; and the prepared N-methylphenethyl ethanolamine and hydrochloride thereof have high yield and high purity, and have high quality.
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- Use of a Catalytic Chiral Leaving Group for Asymmetric Substitutions at sp3-Hybridized Carbon Atoms: Kinetic Resolution of β-Amino Alcohols by p-Methoxybenzylation
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A catalytic strategy was developed for asymmetric substitution reactions at sp3-hybridized carbon atoms by using a chiral alkylating agent generated in situ from trichloroacetimidate and a chiral phosphoric acid. The resulting chiral p-methoxybenzyl phosphate selectively reacts with β-amino alcohols rather than those without a β-NH functionality. The use of an electronically and sterically tuned chiral phosphoric acid enables the kinetic resolution of amino alcohols through p-methoxybenzylation with good enantioselectivity.
- Kuroda, Yusuke,Harada, Shingo,Oonishi, Akinori,Kiyama, Hiroki,Yamaoka, Yousuke,Yamada, Ken-Ichi,Takasu, Kiyosei
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supporting information
p. 13137 - 13141
(2016/10/30)
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- Synthesis of chiral oxazolidinone derivatives through lipase-catalyzed kinetic resolution
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The synthesis of enantioenriched oxazolidinone derivatives through lipase-catalyzed kinetic resolution is described. The synthesis comprised a two-step, cascade acylation in one pot, resulting in a range of oxazolidinone derivatives in good yields and exc
- Zhang, Yan,Zhang, Yang,Ren, Yansong,Ramstr?m, Olof
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- Optimization of immobilization conditions of Mucor miehei lipase onto Florisil via polysuccinimide spacer arm using response surface methodology and application of immobilized lipase in asymmetric acylation of 2-amino-1-phenylethanols
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In this study, the immobilization of Mucor miehei lipase onto Florisil support via polysuccinimide spacer arm was scrutinized by using a 3-factor and 3-level Box-Behnken design. The independent parameters were immobilization pH, immobilization time and initial lipase concentration and the response was the specific activity of immobilized lipase. A quadratic equation was used to explain the relationship between the response and independent parameters. After analysis of variance test, coefficient of determination and adjusted coefficient of determination values were estimated as 0.98 and 0.94, respectively. The optimal immobilization pH, immobilization time and initial lipase concentration were determined as 6.0, 7 h and 1.1 mg mL-1, respectively, after desirability analysis. The specific activity values for three individual experiments were observed as 25.88 ± 0.73, 26.06 ± 0.47 and 25.96 ± 0.52 U mg protein-1 under the optimized conditions. The hydrolytic activities of free and immobilized lipase preparations were characterized using p-nitrophenyl palmitate as substrate. The esterification activity of immobilized lipase preparation was evaluated by asymmetric acylation of 2-(methylamino)-1-phenylethanol, 2-(ethylamino)-1- phenylethanol, 2-(butylamino)-1-phenylethanol, and 2-(hexylamino)-1- phenylethanol with vinyl acetate. The acylation protocol was optimized in terms of the effects of initial water amount, reaction temperature, molar ratio of amino alcohol to vinyl acetate, biocatalyst loading, organic medium and kind of lipases used. The developed protocol provided a facile methodology for the preparation of enantiopure 2-amino-1-phenylethanols which may be used as potential new β-adrenergic receptor antagonists.
- Yildirim, Deniz,Tuekel, S. Seyhan,Alptekin, Oezlem,Alagoez, Dilek
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- Immobilized Pseudomonas sp. lipase: A powerful biocatalyst for asymmetric acylation of (±)-2-amino-1-phenylethanols with vinyl acetate
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Pseudomonas sp. lipase was immobilized onto glutaraldehyde-activated Florisil support via Schiff base formation and stabilized by reducing Schiff base with sodium cyanoborohydride. The immobilization performance was evaluated in terms of bound
- Yildirim, Deniz,Tükel, S. Seyhan
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p. 819 - 830
(2013/07/27)
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- A simple two-step synthesis of 2-(alkylamino)-1-arylethanols, including racemic adrenaline, from aromatic aldehydes via 5-aryloxazolidines
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Benzaldehydes react smoothly with nonstabilized azomethine ylides, generated in situ from sarcosine/formaldehyde or N-(methoxymethyl)-N- (trimethylsilylmethyl)benzylamine, to give 5-aryloxazolidines as intermediates. These were converted into 2-(alkylamino)-1-arylethanols in good yields by simple heating in methanol with hydrochloric acid, or by treatment with hydrazine hydrate in ethanol.
- Moshkin, Vladimir S.,Sosnovskikh, Vyacheslav Ya.
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p. 5869 - 5872
(2013/10/21)
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- Asymmetric hydrogenation of α-primary and secondary amino ketones: Efficient asymmetric syntheses of (-)-arbutamine and (-)-denopamine
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Two ss-receptor agonists (-)-denopamine and (-)-arbutamine were prepared in good yields and enantioselectivities by asymmetric hydrogenation of unprotected amino ketones for the first time by using Rh catalysts bearing electron-donating phosphine ligands. A series of α-primary and secondary amino ketones were synthesized and hydrogenated to produce various 1,2-amino alcohols in good yields and with good enantioselectivies. This Rh electron-donating phosphine-catalyzed asymmetric hyderogenation repI resents one of the most promising and convenient approaches towards the asymmetric synthesis of chiral amino alcohols.
- Shang, Gao,Liu, Duan,Allen, Scott E.,Yang, Qin,Zhang, Xumu
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p. 7780 - 7784
(2008/04/03)
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- Sulfonyl-containing 3,4-diaryl-3-pyrrolin-2-ones, preparation method, and medical use thereof
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The invention relates to sulfonyl-containing 3,4-diaryl-3-pyrrolin-2-ones compounds having formula (I) wherein R1 is selected from the group consisting of 4-methylsulfonyl, 4-aminosulfonyl, hydrogen, 2-, 3-, or 4-halogen, C1-C6
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Page/Page column 4
(2008/06/13)
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- Trifluoroacetamides from amino alcohols as nucleophilic trifluoromethylating reagents
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Both non-enolizable and enolizable carbonyl compounds underwent nucleophilic trifluoromethylation by a new family of cheap and efficient trifluoroacetamide reagents derived from vic-amino alcohols (see picture). From an ecological and an economic viewpoint these represent a promising alternative to other known trifluoromethylation reagents.
- Joubert, Jerome,Roussel, Solveig,Christophe, Carole,Billard, Thierry,Langlois, Bernard R.,Vidal, Thierry
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p. 3133 - 3136
(2007/10/03)
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- α-Aminated methyllithium by DTBB-catalysed lithiation of a N- (chloromethyl) carbamate
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The reaction of O-tert-butyl-N-(chloromethyl)-N-methyl carbamate (1) with lithium powder and a catalytic amount of 4,4'-di-tert-butylbiphenyl (DTBB, 2.5 mol %) in the presence of different electrophiles [Me3SiCl, (i)BuCHO, (t)BuCHO, PhCHO, 4-MeOC6H4CHO, (CH2)4CO, MeCO(n)Pr, Et2CO, MeCO(CH2)2CH=CH2, PhCOMe, PhCO(n)Bu, Ph2CO] in THF at -78°C leads, after hydrolysis with water, to the expected functionalised carbamates 2. Carbamates 2 derived from carbonyl compounds are deprotected with hydrogen chloride (for aromatic aldehyde or ketone derivatives) or with a mixture of phenol and trimethylsilyl chloride (for aliphatic aldehyde derivatives) giving substituted 1,2-diols 4.
- Ortiz, Javier,Guijarro, Albert,Yus, Miguel
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p. 4831 - 4842
(2007/10/03)
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- α-Nitrogenated organolithium compounds from α-amidomethyl and α-aminomethyl sulfones
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Successive reaction of α-amidomethyl sulfones 7a,b, derived from primary amides, with n-butyllithium and primary alkyl bromides (CH2 = CHCH2Br, CH2 = CMeCH2Br, CH2 = CBrCH2Br, CH ≡ CCH
- Alonso, Diego A.,Alonso, Emma,Najera, Carmen,Ramon, Diego J.,Yus, Miguel
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p. 4835 - 4856
(2007/10/03)
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- O-tert-butyl-N-(chloromethyl)-N-methyl carbamate as a source of the MeNHCH2- synthon
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The reaction of O-tert-butyl-N-(chloromethyl)-N-methyl carbamate (1) with lithium powder and a catalytic amount of DTBB (2.5 mol %) in the presence of different electrophiles [Me3SiCl, Bu(i)CHO, Bu(t)CHO, PhCHO, (CH2)4CO, Et2CO, PhCOMe, Ph2CO] in THF at -78°C leads, after hydrolysis with water, to the expected functionalised carbamates 2. As an example, the hydrolysis of compound 2e with hydrogen chloride affords easy deprotection of the amine functionality yielding the corresponding 1,2-aminoalcohol 3e.
- Guijarro, Albert,Ortiz, Javier,Yus, Miguel
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p. 5597 - 5600
(2007/10/03)
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- 1,3 DIPOLAR CYCLOADDITIONS OF AZOMETHINE YLIDES WITH AROMATIC ALDEHYDES. SYNTHESES OF 1-OXAPYRROLIZIDINES AND 1,3-OXAZOLIDINES.
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Substituted 1-oxapyrrolizidines have been synthetized by cycloaddition of azomethine ylides, generated by aldehydes induced decarboxylation of proline, with carbonyl dipolarophyles.The stereochemistry of the cycloadducts indicate that they arise from the
- Orsini, F.,Pelizzoni, F.,Forte, M.,Destro, R.,Gariboldi, P.
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p. 519 - 542
(2007/10/02)
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- Friedel-Crafts Acylation with N-(Trifluoroacetyl)-α-amino Acid Chlorides. Application to the Preparation of β-Arylalkylamines and 3-Substituted 1,2,3,4-Tetrahydroisoquinolines
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Several N-(trifluoroacetyl)-α-amino acid chlorides have been reacted with benzene, anisole, and veratrole in the presence of AlCl3 or SnCl4 to produce the corresponding aromatic ketones in fair to high yields.The products are reductible under neutral or acidic conditions to the corresponding N-(trifluoroacetyl)-β-hydroxy-β-arylakylamines or N-(trifluoroacetyl)-β-arylalkylamines.The latter can be readily detrifluoroacetylated by mild basic hydrolysis and thence converted to the corresponding 3-substituted 1,2,3,4-tetrahydroisoquinolines by condensation with formaldehyde.
- Nordlander, Eric J.,Payne, Mark J.,Njoroge, George F.,Balk, Michael A.,Laikos George D.,Vishwanath, Vasanth M.
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p. 4107 - 4111
(2007/10/02)
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- Neighbour Group Participation with Reductions and Hydride Abstractions
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The reduction of N-(2-hydroxyalkyl)lactams with diisobutylaluminium hydride and the hydride ion abstraction of the corresponding amino alcohols give under neighbour group participation the fused oxazolidines.
- Moehre, H.,Kamper, Ch.
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p. 512 - 520
(2007/10/02)
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- Chemical Constituents of Clausena lansium: Part I-Structure of Lansamide-I and Lansine
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From the leaves of Clausena lansium, β-sitosterol, heptaphylline, lansamide-I and lansine have been isolated.Based on physicochemical studies, the structures of lansamide-I and lansine have been established as N-methyl-N-styrylcinnamide (1) and 3-formyl-2
- Prakash, Dhan,Raj, Kanwal,Kapil, R. S.,Popli, S. P.
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p. 1075 - 1076
(2007/10/02)
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