- An easy stereoselective access to β,γ-aziridino α-amino ester derivatives via Mannich reaction of benzophenone imines of glycine esters with N-sulfonyl α-chloroaldimines
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(Chemical Equation Presented) Mannich-type addition of benzophenone imine glycinates across newly synthesized N-(p-toluenesulfonyl) α- chloroaldimines afforded γ-chloro-α,β-diamino ester derivatives with moderate diastereoselectivity as separable mixtures of anti and syn diastereomers. The γ-chloro-α,β-diamino esters were efficiently cyclized under basic conditions to the corresponding β,γ-aziridino α-amino ester derivatives, representing a new class of conformationally constrained heterocyclic α,β-diamino acid derivatives. The relative configuration of the aziridines was determined via X-ray diffraction analysis. Mechanisms and intermediate transition states to explain the stereochemical outcome of the Mannich reaction with different substrates or under different conditions are proposed. The synthetic importance of the β,γ- aziridino α-amino ester derivatives is demonstrated by their conversion into the corresponding Boc-protected derivatives and ring opening reactions to α,β-diamino esters and a γ-amino α,β-unsaturated amino ester.
- Kiss, Lorand,Mangelinckx, Sven,Sillanpaeae, Reijo,Fueloep, Ferenc,De Kimpe, Norbert
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- Alkenyl Exchange of Allylamines via Nickel(0)-Catalyzed C-C Bond Cleavage
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A functional group exchange reaction between allylamines and alkenes via nickel-catalyzed C - C bond cleavage and formation was developed. This reaction provides a novel protocol, which does not require the use of unstable imine substrates, for the synthesis of allylamines, which are widely used in the production of fine chemicals, pharmaceuticals, and agrochemicals.
- Fan, Chao,Lv, Xin-Yang,Xiao, Li-Jun,Xie, Jian-Hua,Zhou, Qi-Lin
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p. 2889 - 2893
(2019/02/19)
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- The Generation of Difluoroketenimine and Its Application in the Synthesis of α,α-Difluoro-β-amino Amides
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Fluorine-containing β-amino acids and their derivatives have attracted significant attention due to their importance in life sciences. Herein the previously unknown difluoroketenimine, the analogue of the elusive difluoroketene, has been generated by the
- Zhang, Rui,Zhang, Zhikun,Zhou, Qi,Yu, Lefei,Wang, Jianbo
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p. 5744 - 5748
(2019/03/28)
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- NHC ligand-enabled Ni-catalyzed reductive coupling of alkynes and imines using isopropanol as a reductant
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A nickel-catalyzed reductive coupling of alkynes and imines using readily available isopropanol as the reducing agent was developed. The use of a sterically bulky and electron-rich carbene ligand (AnIPr) significantly promotes the reaction, providing various multi-substituted allylic amines in 23-89% yield and the corresponding chiral ligand (AnIPr-3) can afford the products in 51-95% ee.
- Yao, Wei-Wei,Li, Ran,Li, Jiang-Fei,Sun, Juan,Ye, Mengchun
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supporting information
p. 2240 - 2244
(2019/05/17)
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- Palladium-Catalyzed Direct Intramolecular C-N Bond Formation: Access to Multisubstituted Dihydropyrroles
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A palladium-catalyzed intramolecular amination of alkenes with retention of olefin functionalization was achieved under mild reaction conditions. In the presence of palladium catalyst, the tosyl-protected amine can directly couple with a double bond to provide versatile dihydropyrrole derivatives in moderate to excellent yields.
- Jiang, Bing,Meng, Fei-Fan,Liang, Qiu-Ju,Xu, Yun-He,Loh, Teck-Peng
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p. 914 - 917
(2017/02/26)
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- Asymmetric Arylation of Imines Catalyzed by Heterogeneous Chiral Rhodium Nanoparticles
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Asymmetric arylation of aldimines catalyzed by heterogeneous chiral rhodium nanoparticles has been developed. The reaction proceeded in aqueous media without significant decomposition of the imines by hydrolysis to afford chiral (diarylmethyl)amines in high yields with outstanding enantioselectivities. This catalyst system exhibited the highest turnover number (700) in heterogeneous catalysts reported to date for these reactions. The reusability of the catalyst was also demonstrated.
- Yasukawa, Tomohiro,Kuremoto, Tatsuya,Miyamura, Hiroyuki,Kobayashi, Sh?
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supporting information
p. 2716 - 2718
(2016/06/15)
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- Aza-Morita-Baylis-Hillman reactions catalyzed by a cyclopropenylidene
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Catalysis using a bis(dialkylamino)cyclopropenylidene (BAC) has been developed, which relies on a formal umpolung activation of Michael acceptor pro-nucleophiles. Various aza-Morita-Baylis-Hillman reactions between aromatic, heteroaromatic, or aliphatic imines and acyclic or cyclic α,β-unsaturated ketones and carboxylic acid derivatives have been catalyzed by a BAC under mild conditions. Functionalities such as unprotected amino and hydroxy groups have been tolerated. The catalyst loading was decreased to 1 mol% without loss of activity. The BAC catalyst was shown to be substantially more active than a cyclic (alkyl)(amino) carbene (CAAC), N-heterocyclic carbenes (NHCs), and P- or N-centered Lewis bases.
- Lu, Xun,Schneider, Uwe
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supporting information
p. 12980 - 12983
(2016/11/09)
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- Chemoselective Boron-Catalyzed Nucleophilic Activation of Carboxylic Acids for Mannich-Type Reactions
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The carboxyl group (COOH) is an omnipresent functional group in organic molecules, and its direct catalytic activation represents an attractive synthetic method. Herein, we describe the first example of a direct catalytic nucleophilic activation of carbox
- Morita, Yuya,Yamamoto, Tomohiro,Nagai, Hideoki,Shimizu, Yohei,Kanai, Motomu
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p. 7075 - 7078
(2015/06/25)
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- Aza-Reformatsky reaction promoted by catalytic samarium diiodide: Synthesis of β-amino esters or amides
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The synthesis of β-amino esters or amides has been achieved from moderate to high yields from the reaction of imines and α-halo esters or amides promoted by catalytic amounts of samarium diiodide in the presence of magnesium turnings as co-reductant. A me
- Rodríguez-Solla, Humberto,Díaz-Pardo, Ainhoa,Concellón, Carmen,Del Amo, Vicente
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p. 1709 - 1712
(2014/08/05)
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- A Mannich/cyclization cascade process for the asymmetric synthesis of spirocyclic thioimidazolidineoxindoles
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An asymmetric cascade Mannich/cyclization reaction between 3-isothiocyanato oxindoles and sulfimides using a commercially available organocatalyst has been developed. A wide range of structurally diverse spiro[imidazolidine-4,3′-oxindole] derivatives were
- Cai, Hao,Zhou, Yu,Zhang, Dong,Xu, Jinyi,Liu, Hong
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supporting information
p. 14771 - 14774
(2015/01/09)
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- Rhodium-catalyzed direct addition of indoles to N-sulfonylaldimines
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The rhodium-catalyzed addition of indole C-H bonds to a range of aryl- and alkyl-N-sulfonylaldimines is reported. The reaction proceeds with high functional group compatibility and provides easy and rapid access to a wide variety of 2-indolylmethanamine derivatives under mild reaction conditions.
- Zhou, Bing,Yang, Yaxi,Lin, Sui,Li, Yuanchao
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supporting information
p. 360 - 364
(2013/05/08)
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- One-pot preparation of homopropargylic N-sulfonylamines catalyzed by zinc powder
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A new one-pot method for synthesis of homopropargylic N-sulfonylamines from aldehydes catalyzed by zinc powder is described. The procedure is lauded by its simplicity, good yields, and adaptability to a wide variety of aldehydes.
- Wu, Chao,Huang, Wangyong,He, Weimin,Xiang, Jiannan
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supporting information
p. 1233 - 1234
(2013/10/22)
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- Chiral diphosphane- and NHC-containing ruthenium catalysts for the catalytic asymmetric arylation of aldimines with organoboron reagents
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For the first time, we report the application of [RuCl2(η 6-p-cymene)]2 in the arylation of N-activated aldimines with boronic acids and its derivatives to afford chiral amines, which are important intermediates in the syntheses of key bioactive compounds. The behavior of the chiral ligands, the imine substrates, and the organoboron reagents were studied. Very good enantioselectivities were obtained. A new method is presented for the synthesis of chiral substituted amines by employing Ru catalysts along with known chiral phosphane ligands and a new NHC-type chiral ligand. Organoboron reagents were applied as the aryl transfer agents. High enantioselectivities were achieved with this new method, and some mechanistic insights are provided.
- Marques, Carolina S.,Burke, Anthony J.
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supporting information; experimental part
p. 4232 - 4239
(2012/09/22)
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- The use of samarium or sodium iodide salts as an alternative for the aza-Henry reaction
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A novel reaction of bromonitromethane with a variety of imines in very mild conditions promoted by SmI2 and NaI to afford nitroamines or bromonitroamines is described. When these reactions were performed on sugar-based imines, the corresponding
- Rodríguez-Solla, Humberto,Concellón, Carmen,Alvaredo, Noemí,Soengas, Raquel G.
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experimental part
p. 1736 - 1744
(2012/03/10)
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- Highly enantioselective arylation of N -tosylalkylaldimines catalyzed by rhodium-diene complexes
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A highly enantioselective rhodium-catalyzed arylation of aliphatic N-tosylaldimines has been developed. The combination of chiral bicyclo[3.3.0]octadiene ligands, an active rhodium hydroxide complex, and neutral reaction conditions is the key to achieving high yield and enantioselectivity. The application of this method is demonstrated by the enantioselective synthesis of chiral 2-aryl pyrrolidines and piperidines in a one-pot procedure. Furthermore, excellent results are also obtained for the imine substrates with the more readily cleavable N-nosyl protecting group.
- Cui, Zhe,Yu, Hong-Jie,Yang, Rui-Feng,Gao, Wen-Yun,Feng, Chen-Guo,Lin, Guo-Qiang
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supporting information; experimental part
p. 12394 - 12397
(2011/10/02)
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- Synthesis of α-sulfanyl-β-amino acid derivatives by using nanocrystalline magnesium oxide
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The Mannich-type reaction between alkyl, aryl and heterocyclic aldimines and sulfonium salts for the synthesis of α-sulfanyl-β-amino acid derivatives by using nanocrystalline magnesium oxide (NAP-MgO) is described. These products are obtained in moderate to high yields with moderate diastereoselectivities. The configuration of ethyl-3-{[(4-methylphenyl)sulfonyl] amino}-2-(methylsulfanyl)-3-(4-nitrophenyl)propanoate (major isomer) has been confirmed by X-ray diffraction technique to be anti, and consistent with the assignment based on 1H NMR spectroscopy. These α-sulfanyl- β-amino acid derivatives are important building blocks for pharmaceuticals with potent biological activity.
- Kantam, M. Lakshmi,Mahendar, Koosam,Sreedhar, Bojja,Choudary, Boyapati. M.,Bhargava, Suresh K.,Priver, Steven H.
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experimental part
p. 5042 - 5052
(2010/08/20)
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- Iron-catalyzed sulfonylimine synthesis under neutral conditions
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A convenient FeCl3-catalyzed synthesis of N-sulfonylimines via the condensation of aldehydes with N-sulfonylamides in mild and neutral conditions (in ethanol at room temperature) is reported. This procedure constitutes the first iron-catalyzed
- Wu, Xiao-Feng,Vovard-Le Bray, Chloé,Bechki, Lazhar,Darcel, Christophe
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experimental part
p. 7380 - 7384
(2009/12/06)
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- Direct synthesis of aliphatic vinyl aziridines
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The synthesis of vinyl aziridines, by the reactions of a range of diphenylphosphinyl and p-toluenesulfonyl alkyl aldimines with the ylide derived from S-allyl tetrahydrothiophenium bromide, are reported.
- Arini, Louise G.,Sinclair, Alex,Szeto, Peter,Stockman, Robert A.
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p. 1589 - 1591
(2007/10/03)
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- A stereoselective synthesis of alkynylaziridines
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Reactions between allenylzinc carbenoid 1 and various imines were examined; trans-substituted alkynylaziridines were produced with excellent diastereoselectivity. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
- Chemla, Fabrice,Ferreira, Franck,Hebbe, Virginie,Stercklen, Eric
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p. 1385 - 1391
(2007/10/03)
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