- The first enzyme-promoted addition of nitromethane to imines (aza-Henry reaction)
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Enzyme catalytic promiscuity is the ability of a single enzyme active site to catalyze several chemical transformations, among them those which are different from natural. We have attempted to use this feature of enzymes in the nucleophilic addition of nitromethane to aldimines (the aza-Henry reaction) whose chemically catalyzed version leads to synthetically useful β-nitroamines. We succeded in obtaining for the first time the desired products in the yields up to 81%. The most efficient proved lipase TL (from Pseudomonas stutzeri) and oxynitrilase from Arabidopsis thaliana. However, all the reactions investigated were non-stereoselective.
- Janicki, Ignacy,?y?wa, Piotr,Kie?basiński, Piotr
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- Domino Synthesis of 3-Alkyliden-2,3-Dihydro-4-Quinolones
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The synthesis of 3-alkyliden-2,3-dihydro-4-quinolones has been accomplished in a domino fashion through a three-step sequence that comprised an initial aza-Baylis-Hillman reaction, followed by a 1,3-rearrangement and an intramolecular amination. Starting from readily available aryl vinyl ketones and N-tosyl imines, the reaction with PPh3, CsOAc and CuI in CH3CN gave rise, in good overall yields, to final 3-alkyliden-4-quinolone derivatives, valuable scaffolds in medicinal chemistry. The simultaneous addition of two bases, PPh3 and CsOAc, was found to be crucial for the success of the process. While PPh3 promoted the reversible aza-Baylis-Hillman reaction, CsOAc triggered the subsequent 1,3-rearrangement, which shifted the initial equilibrium and allowed to complete the synthetic sequence upon the addition of CuI. (Figure presented.).
- Raga, Esther,Escolano, Marcos,Torres, Javier,Rabasa-Alca?iz, Fernando,Sánchez-Roselló, María,del Pozo, Carlos
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supporting information
p. 1102 - 1107
(2019/01/30)
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- Silica-supported zinc chloride (ZnCl2/SiO2)-induced efficient protocol for the synthesis of N-sulfonyl imines and 2-Arylbenzothiazole
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A straightforward strategy for the synthesis of N-sulfonyl imine derivatives from sulfonamides and aryl aldehydes utilizing Silica-supported zinc chloride (ZnCl2/SiO2, silzic) as a catalyst under solvent-free conditions has been developed. 2-Arylbenzothiazole derivatives were also synthesized by the reaction of 2-aminothiophenol with aryl aldehydes under the same conditions. This procedure has advantages of high yields, mild reaction condition, simple procedure, low cost, and simplicity of workup. The catalyst has the same efficiency on its reuse up to three times.
- Soliman, Hanan A.,El-Shahat, Mahmoud,Soliman, Abdel-Ghany
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p. 584 - 591
(2019/07/31)
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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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- Enantioselective Aza-Reformatsky Reaction with Ketimines
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Here, an enantioselective aza-Reformatsky reaction using acyclic ketimine substrates is presented. Using α-phosphorated ketimines as electrophilic substrates and a simple BINOL-derived ligand, phosphorated analogues of aspartic acid holding chiral tetrasubstituted carbons are efficiently obtained with excellent enantioselectivity through an asymmetric organocatalytic Reformatsky-type reaction. The phosphorated analogues of aspartic acid have been used for the synthesis of phosphorus-containing enantiopure tetrasubstituted β-lactams.
- Maestro, Aitor,Martinez De Marigorta, Edorta,Palacios, Francisco,Vicario, Javier
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supporting information
p. 9473 - 9477
(2019/11/28)
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- Synthesis of novel N-(p-toluenesulfonyl)aminophosphonates and evaluation of their biological properties
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The synthesis of a series of N-sulfonylaminophosphonates 2aA-2dC and evaluation of their cytotoxicity and ecotoxicity is described. N-sulfonylaminophsophonates 2aA-2dC were obtained by addition of dialkyl phosphites to azomethine bonds of sulfonimines 1a-
- Karpowicz, Rafa?,Lewkowski, Jaros?aw,Stasiak, Ma?gorzata,Czopor, Aleksandra,Tokarz, Paulina,Król, Adrianna,Rogacz, Diana,Rychter, Piotr
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p. 423 - 436
(2018/02/06)
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- Synthesis of Benzyl Amines via Copper-Catalyzed Enantioselective Aza-Friedel-Crafts Addition of Phenols to N -Sulfonyl Aldimines
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A new copper-catalyzed enantioselective aza-Freidel-Crafts reaction between phenols and N-sulfonyl aldimines that provides chiral secondary benzylamines in good to excellent yields and excellent enantioselectivities (up to 99% ee) is disclosed. In particular, excellent scope with alkylimines was observed for the first time. The synthetic utility of the products was demonstrated in the first enantioselective synthesis of a dual orexin receptor antagonist, a compound that contains an amine-bearing stereocenter adjacent to a bis-ortho-functionalized arene.
- Shikora, Jonathan M.,Chemler, Sherry R.
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supporting information
p. 2133 - 2137
(2018/04/30)
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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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supporting information
p. 7075 - 7078
(2015/06/25)
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- A gold-catalyzed 1,2-acyloxy migration/intramolecular cyclopropanation/ring enlargement cascade: Syntheses of medium-sized heterocycles
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The synthesis of medium-sized heterocycles possessing a trans double bond is still a challenge. Herein, gold(I)-catalyzed 1,2-acyloxy migration/intramolecular cyclopropanation/ring enlargement cascade reaction of furans has been developed, providing highly efficient access to ten- and eleven-membered heterocycles with a broad substrate scope under mild reaction conditions. The reaction outcome features high chemoselectivity at the C5-position of furan. Moreover, a trans-double bond was embodied in the medium ring system.
- Sun, Yin-Wei,Tang, Xiang-Ying,Shi, Min
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supporting information
p. 13937 - 13940
(2015/09/07)
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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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- Synthesis of di-, tri-, and tetrasubstituted pyridines from (phenylthio)carboxylic acids and 2-[aryl(tosylimino)methyl]acrylates
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An isothiourea-catalyzed Michael addition-lactamization followed by the sulfide oxidation-elimination/N- to O-sulfonyl transfer sequence for the formation of 2,3,5- and 2,3-substituted pyridine 6-tosylates from (phenylthio)acetic acids and α,β-unsaturated
- Stark, Daniel G.,O'Riordan, Timothy J. C.,Smith, Andrew D.
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supporting information
p. 6496 - 6499
(2015/02/05)
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- A multicomponent approach to the synthesis of N-sulfonyl β2,3-amino esters
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The multicomponent synthesis of α,β-disubstituted N-sulfonyl β-amino esters is described. It involves a zinc-mediated, cobalt-catalyzed three-component reaction between sulfonylimines, acrylates and organic bromides. A possible mechanism is proposed, emph
- Gall, Erwan Le,Sengmany, Stephane,Samb, Issa,Benakrour, Sabrina,Colin, Christopher,Pignon, Antoine,Leonel, Eric
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supporting information
p. 3423 - 3426
(2014/05/20)
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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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- Rhodium-catalyzed synthesis of branched amines by direct addition of benzamides to imines
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Rhodium-catalyzed addition of benzamide C-H bonds to a range of aromatic N-sulfonyl aldimines has been developed and proceeds with high functional group compatibility. The synthetic utility of the resulting branched amine products has also been demonstrated by the preparation of isoindoline and isoindolinone frameworks.
- Hesp, Kevin D.,Bergman, Robert G.,Ellman, Jonathan A.
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supporting information; experimental part
p. 2304 - 2307
(2012/06/30)
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- Dinuclear zinc catalyzed asymmetric Friedel-Crafts amidoalkylation of indoles with aryl aldimines
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The asymmetric Friedel-Crafts amidoalkylation of indoles with aryl aldimines could be efficiently catalyzed by Trost's bis-ProPhenol dinuclear zinc complexes to attain 3-indolyl methanamine derivatives in good to excellent yields (85-98%) with moderate to high enantiomeric ratios (from 70:30 up to 95:5 er). Remarkably, this approach provides efficient access to enantiomerically enriched 3-indolyl methanamines, which avoids the formation of the undesirable bis- and tris(indolyl)methanes (BIMs and TIMs) byproduct.
- Wang, Bei-Lei,Li, Nai-Kai,Zhang, Jin-Xin,Liu, Guo-Gui,Liu, Teng,Shen, Qi,Wang, Xing-Wang
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supporting information; experimental part
p. 2614 - 2617
(2011/05/08)
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- One-pot nitro-Mannich/hydroamination cascades for the direct synthesis of 2,5-disubstituted pyrroles using base and gold catalysis
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An efficient, easy to perform, one-pot reaction cascade for the synthesis of 2,5-disubstituted pyrroles from p-toluenesulfonyl protected imines and 4-nitrobut-1-yne under a combination of base and gold(iii) catalysis is reported.
- Barber, David M.,Sanganee, Hitesh,Dixon, Darren J.
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supporting information; body text
p. 4379 - 4381
(2011/06/17)
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- Organic hydrogen phosphites and hydrogen phosphates catalyzed Friedel-Crafts amidoalkylation of indoles with aryl aldimines
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A highly efficient and selective Friedel-Crafts amidoalkylation reaction of indoles with N-Ts aryl aldimines has been developed utilizing dimethyl hydrogen phosphite or diphenyl hydrogen phosphate as the organocatalysts, providing a facile and cost-effect
- Wang, Bei-Lei,Zhang, Jin-Xin,Li, Nai-Kai,Liu, Guo-Gui,Shen, Qi,Wang, Xing-Wang
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supporting information; experimental part
p. 4671 - 4674
(2011/10/01)
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- Base-promoted selective β-fragmentation of homoallylamines
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A selective β-fragmentation of homoallylamines with the combination of iodobenzene diacetate, iodine, and sodium acetate is reported. The desired carbon-carbon bond cleavage proceeded via a radical β-scission pathway under mild conditions with good functional group tolerance.
- Li, Weixun,Gan, Jianhong,Fan, Renhua
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experimental part
p. 4275 - 4277
(2010/09/07)
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- The reaction of N-tosyl imines with heteroaromatic compounds: A new access to triheteroarylmethanes
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Useful triheteroarylmethanes were prepared by the double Friedel-Crafts reaction of a wide variety of aromatic N-tosyl imines with furan, thiophene, and pyrrole in the presence of Cu(OTf)2 and Montmorillonite K-10 clay catalysts.
- Temelli, Baris,Tasgin, Dilek Isik,Unaleroglu, Canan
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body text
p. 6765 - 6768
(2010/10/01)
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- SmI2-coupling reaction of chiral non-racemic α-bromo-α′-sulfinyl ketones with imines: synthesis of enantiomerically pure 2-methyl-3-amino-1-ol moieties
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Chiral non-racemic α-bromo-α′-sulfinyl ketones were shown to react with imines in the presence of SmI2 to give the corresponding 1,3-aminoketo derivatives with good syn-diastereoselectivity. Further reduction of these adducts either with DIBAL-
- Barbarotto, Marie,Geist, Julie,Choppin, Sabine,Colobert, Francoise
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experimental part
p. 2780 - 2787
(2010/03/30)
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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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- New access to trisubstitutea 3-pyrrolines under phosphine catalysis
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Conjugated dienes, properly activated by electron-withdrawing groups on both ends, are shown to be suitable substrates for phosphinepromoted organocatalytic processes. Their reactions with imines, under phosphine catalysis, afford a new and efficient synthetic approach to functionalized 3-pyrrolines.
- Schuler, Marie,Duvvuru, Deepti,Retailleau, Pascal,Betzer, Jean-Francois,Marinetti, Angela
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supporting information; experimental part
p. 4406 - 4409
(2009/12/26)
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- A novel method for the synthesis of N-sulfonylaldimines by ZnO as a recyclable neutral catalyst under solvent-free conditions
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ZnO acts as an effective catalyst for the rapid synthesis of a range of N-sulfonylaldimines from aromatic aldehydes and sulfonamides under solvent free conditions. The ZnO powder can be reused up to three times after simple washing with distilled water and ethyl acetate.
- Hosseini-Sarvari, Mona,Sharghi, Hashem
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p. 2125 - 2130
(2008/02/08)
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