1. The first enantioselective vinylogous Mannich reaction is developed using 2-methoxyfuran under chiral spirophosphoric acid catalysis. The strategy involves 4-isoxazoline derivatives as cyclic ketimine surrogates and provides γ- butenolide scaffolds (up to 97% ee and >20:1 dr). The mechanistic investigations suggest that an in situ generated water molecule plays a crucial role in delivering γ-butenolide, while the use of molecular sieves delivers aza-Friedel−Crafts products. The synthetic utility of γ-butenolide is shown toward obtaining piperidone skeleton via a lactone-lactam rearrangement.
  2. An asymmetric organocatalytic aza-Friedel-Crafts reaction was developed to give the enantioenriched Δ4 -isoxazoline scaffold bearing a quaternary-substituted stereogenic centre in goodto-excellent yields and enantioselectivity (50–99%, 55–>99% ee). This protocol involves the in situ generated isoxazolium ions in the presence of a chiral phosphoric acid followed by the heteroarene addition through asymmetric counteranion-directed catalysis.
  3. A regioselective [3+2] cyclisation reaction between 2-arylidene-1,3-indanedione and ethyl 2,3- butadienoate catalysed by triphenylphosphine has been demonstrated to synthesize functionalised spirocyclic cyclopentenes. The reaction tolerated various electron-rich and electron-deficient aryl substituted 2-arylidene-1,3-indanediones with high to excellent chemical yields (up to 99%) and moderate to good regioselectivity (up to 5 : 1). DFT studies have also been carried out to understand the regioselective nature of this reaction. The results of Frontier molecular orbital calculations and the activation energy (Ea) favour the formation of compound 3a via g-attack compared to that of 4a via aattack.
  4. To construct multisubstituted seven-membered nitrogenous heterocyclic scaffolds, an efficient method, employing 2-aminoaryl N-monosubstituted hydrazones and 2-oxo-3-butenoates under Brønsted acid catalysis, has been developed. This strategy highlights the umpolung reactivity of 2-aminobenzaldehyde arylhydrazones toward 2-oxo-3-butenoates to afford (E)- diazoaryl-benzo[b]azepine derivatives in excellent yields (89−99%) and with high diastereoselectivi
  5. An organocatalytic enantioselective synthesis of δ-lactone-fused 4-chromanones was demonstrated using 1-(2-hydroxyaryl)-1,3-butanedione and α,β-unsaturated aldehydes in the presence of the Jørgensen-Hayashi catalyst. The reaction proceeded through a Michael addition/cycloketalization/hemiacetalization sequence, and the resulting hemiacetals were oxidized into the corresponding lactone derivatives in a one-pot manner. The
  6. An efficient organocatalytic cascade reaction for synthesising functionalized bicyclic nitrones is reported. The reaction of dielectrophilic ethyl 2-(nitromethylene)-4-arylbut-3-ynoate and (E)-diethyl 2-((2-hydroxybenzylidene)-amino)malonates to give a unique nitrone scaffold in the presence of a catalytic amount of DABCO is described. The working mechanism was proposed to proceed with allene formation followed by intramolecular cyclization and the rearrangement of an oxygen atom in the nitro group. A broad range of substrates was accessed in this facile chemical transformation, in which the bicyclic nitrones were isolated in moderate to good yields (19% to 79%) with excellent diastereoselectivity (>20:1 dr).
  7. Metal-free addition of salicylhydrazones to electron deficient internal alkynes catalyzed by 1,4-diazabicyclo[2.2.2]octane (DABCO) to yield oxa-bridged 2,6-epoxybenzo[b][1,5]oxazocine heterocycles was achieved. The demonstrated protocol proceeds through an o-quinone methide formation, aza-Michael addition, stereoselective protonation, enamine promoted aromatization, O,O-acetalization and O,N-aminalization sequence to provide privileged heterocycles in good yields with high diastereoselectivities.
  8. An efficient diastereoselective strategy to access complex
  9. The Morita–Baylis–Hillman (MBH) reaction is one of the most useful and efficient protocols for constructing new carbon–carbon bonds between an activated olefin and electrophiles in the presence of a tertiary amine/phosphine. Herein, we present the use of MBH alcohols, which are obtained from the reaction of nitrostyrenes with aldehydes, as well as acetates and amines derived thereof in several organocatalytic transformations. Densely functionalised MBH adducts can also be used to synthesise substituted heteroaromatic compounds, such as furan, pyrrole, pyrazole and imidazole derivatives.
  10. This minireview described an organocatalytic kinetic resolution (OCKR) that was evolved on the basis of using small organic catalysts via an enamine/iminium, N-heterocycle carbene and hydrogen bonding catalysis. The review was embedded using recent methodologies in which the evolution of the OCKR mainly involved creating new stereogenic centre(s) in functionalized products through the formation of a C-C, C-N, C-O, C-X or C-S bond. The combination of the OCKR with sequential reactions and its association with desymmetrisation, and dynamic kinetic resolution are also described.
  11. Kinetic resolution of functionalized nitroallylic amines was established by using chiral α,α-L-diphenylprolinol silyl ether auxiliary through isolation of the dihydrooxazine N-oxide intermediates. The less reactive (S)-nitroallylic amines were obtained with high optical purities. Further hydrolysis of the resting intermediates provided the enantioenriched tetrahydropyridines in high chemical yields with high to excellent levels of diastereo- and enantioselectivities (up to >20:1 dr and 99:1 er). Detailed mechanistic explanation was probed computationally for site of protonation in dihydrooxazine intermediate. The diastereoselective protonation that proceeded concurrently with the heterocyclic ring opening asynchronously was proposed. The hydrolysed reactions were monitored through NMR studies and results were delineated. The one pot catalytic strategy was attempted to give the corresponding substituted tetrahydropyridine derivatives with good to high stereoselectivities.
  12. An efficient organocatalytic reaction
  13. Recent advances in organocatalytic kinetic resolution by using small organic catalysts to resolve various racemates are described. The combination of sequential reaction processes and organocatalytic kinetic resolution enables the functionalization of products for further elaboration and recovery of less kinetically favored substrates to maximize atom economy.
  14. An efficient organocatalytic method was developed for synthesizing functionalized spiropyrazolone derivatives containing four contiguous stereogenic centres by using a Michael-aldol consecutive reaction. We applied a quinine-derived squaramide catalyst to catalyze a reaction between 3-methyl-1-aryl-2-pyrazolin-5-ones and (E)-5-nitro-6-aryl-hex-5-en-2-ones, realizing the desired spiropyrazolones in moderate-to-good yields (up to 80%) with good-to-excellent stereoselectivities (up to >20:1 : dr, 94% ee).
  15. An efficient organocascade quadruple reaction was conducted to
  16. An organocatalytic kinetic resolution of racemic secondary nitroallylic alcohols.....必填欄位
  17. Yi-Ya Zhanga, Ramani Gurubrahamama and Kwunmin Chen* “Rauhut-Currier-Initiated Organocascade Reaction: Synthesis of Substituted Dispirocyclohexanes through [2+2+2] Strategy Between 2-Arylideneindan-1,3-diones and Activated Alkenes” Adv. Synth. Catal. 2015, 357, 2457-2463.
  18. The paper presents an efficient and stereoselective method for constructing spirocyclohexane indane-1,3-diones. This method is based on a chiral squaramide-catalysed highly diastereo- and enantioselective cascade Michael–aldol reaction between γ-nitro ketones and 2-arylidene-1,3-indanedione that affords functionalised spirocyclohexane products in high chemical yields with the formation of three stereogenic centres (57-97%; up to >20:1 dr and 86% ee).
  19. This study describes an organocatalytic kinetic resolution of racemic secondary nitroallylic alcohols (2) combined with simultaneous desymmetrization of prochiral cyclic anhydrides (1). The experimental results revealed that enantioselective alcoholysis of 3-substituted glutaric anhydrides afforded hemiesters (3) with high levels of enantioselectivities (up to 99% ee) in the presence of cinchonidine-derived thiourea catalyst (IV). The highly optical enrichment (up to 95% ee) of (S)-nitroallylic alcohols (2) were recovered.
  20. An organocatalytic domino reaction between 2-arylidane
  21. The direct organocatalytic desymmetrization of cyclic meso-anhydrides was achieved by alcoholysis with nitroallylic alcohols. The reaction between primary nitroallylic alcohols and cyclic meso-anhydrides catalyzed by cinchonidine derived thiourea organocatalyst II (10 mol%) proceeded smoothly. The corresponding hemiesters were obtained in high chemical yields with high to excellent levels of stereoselectivity (up to 90% yield and 99% ee). On the other hand, the reversal of enantioselectivity was observed when an amino cinchonidine derivative (III) was used as the organocatalyst under the similar reaction conditions. This demonstrated an example of activation of the nucelophilic component in the desymmetrization of cyclic meso-anhydrides. 2014 Elsevier Ltd. All rights reserved.
  22. The organocatalytic desymmetrization was demonstrated for 4-substituted cyclohexanones by

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