- Catalytic Reductive Cross-Coupling between Aromatic Aldehydes and Arylnitriles
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A reductive cross-coupling reaction between aromatic aldehydes and arylnitriles using a copper catalyst and a silylboronate as a reductant is reported. This protocol represents an unprecedented approach to the chemoselective synthesis of α-hydroxy ketones by electrophile–electrophile cross-coupling.
- Mitsui, Atsuhisa,Nagao, Kazunori,Ohmiya, Hirohisa
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p. 7094 - 7098
(2021/04/16)
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- Copper-Catalyzed Enantioselective Reductive Cross-Coupling of Aldehydes and Imines
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A copper-catalyzed enantioselective reductive cross-coupling using aromatic aldehydes and imines, producing chiral β-amino alcohols, is described. The catalytic formation of enantioenriched chiral α-alkoxyalkylcopper(I) species from aromatic aldehydes and the subsequent reaction with imine electrophiles are attractive features of this protocol.
- Mitsui, Atsuhisa,Nagao, Kazunori,Ohmiya, Hirohisa
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supporting information
(2020/02/04)
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- Reductive coupling between aromatic aldehydes and ketones or imines by copper catalysis
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The copper-catalyzed reductive coupling of two different carbonyl compounds has been achieved. The reaction of aromatic aldehydes and arylketones with a silylboronate in the presence of a catalytic amount of a CuCl-N-heterocyclic carbene (NHC) complex and a stoichiometric amount of alkoxide base yielded cross-coupled 1,2-diol derivatives. A reaction pathway is proposed that involves the catalytic formation of a nucleophilic α-silyloxybenzylcopper(I) species from the aromatic aldehyde and its subsequent coupling with the arylketone. This process was amenable to asymmetric catalysis. This copper catalyst system also enabled the reductive coupling between aromatic aldehydes and imines.
- Takeda, Mitsutaka,Mitsui, Atsuhisa,Nagao, Kazunori,Ohmiya, Hirohisa
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supporting information
p. 3664 - 3669
(2019/02/14)
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- Mesoporous Titania-Iron(III) Oxide with Nanoscale Porosity and High Catalytic Activity for the Synthesis of β-Amino Alcohols and Benzimidazole Derivatives
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A mesoporous TiO2-Fe2O3 mixed oxide material (MTF-1E) with nanoscale porosity and a high BET surface area was synthesized using sodium dodecyl sulfate (SDS) as a structure-directing agent. The material was characterized by
- Roy, Susmita,Banerjee, Biplab,Salam, Noor,Bhaumik, Asim,Islam, Sk. Manirul
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p. 2689 - 2697
(2015/09/15)
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- Fe(OH)3 nano solid material: An efficient catalyst for regioselective ring opening of aryloxy epoxide with amines under solvent free condition
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Iron hydroxide-Fe(OH)3and iron oxides (Fe3O4and Fe2O3) were successfully prepared and characterized. These materials were employed as efficient and environmentally benign heterogeneous catalysts for t
- Shah, Arpan K.,Prathap, K. Jeya,Kumar, Manish,Abdi, Sayed H.R.,Kureshy, Rukhsana I.,Khan, Noor-ul H.,Bajaj, Hari C.
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p. 442 - 450
(2017/02/05)
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- Enantioselective ring-opening of meso-epoxides by aromatic amines catalyzed by a homochiral metal-organic framework
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The enantioselective ring-opening of meso-epoxides by aromatic amines was achieved by using a new chiral metal-organic framework UTSA-32a. The corresponding α-hydroxyamines were obtained with good yields and ee values (up to 89% ee).
- Regati, Sridhar,He, Yabing,Thimmaiah, Muralidhara,Li, Peng,Xiang, Shengchang,Chen, Banglin,Zhao, John Cong-Gui
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p. 9836 - 9838
(2013/10/21)
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- Asymmetric ring opening of meso-epoxides with aromatic amines using (R)-(+)-BINOL-Sc(OTf)3-NMM complex as an efficient catalyst
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This work reports the asymmetric ring-opening reaction of meso-epoxides with aromatic amines by using the highly efficient in situ generated (R)-(+)-BINOL-Sc(OTf)3-N-methylmorpholine complex. The asymmetric ring opening of cis-stilbene oxide wi
- More, Ganesh V.,Bhanage, Bhalchandra M.
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p. 6900 - 6906
(2013/11/06)
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- Titanium-mediated cross-coupling reactions of imines with ketones or aldehydes: An efficient route for the synthesis of 1,2-amino alcohols
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The cross-coupling reactions of imines with ketones using Ti(O iPr)4/c-C5H9MgCl reagent lead to 1,2-amino alcohols after hydrolysis. The coupling reactions with aldehydes could also afford 1,2-amino alcohols, however, in some cases, aziridines were obtained as major products in a stereoselective manner.
- Fan, Guoqin,Liu, Yuanhong
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supporting information; experimental part
p. 5084 - 5087
(2012/09/25)
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- Zinc tetrafluoroborate hydrate as a mild catalyst for epoxide ring opening with amines: Scope and limitations of metal tetrafluoroborates and applications in the synthesis of antihypertensive drugs (RS)/(R)/(S)-metoprolols
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The scope and limitations of metal tetrafluoroborates have been studied for epoxide ring-opening reaction with amines, and Zn(BF4) 2?xH2O has been found to be a mild and efficient catalyst affording high yields under solvent-free conditions at rt with excellent chemo-, regio-, and stereoselectivities. The catalytic efficiency followed the order Zn(BF4)2?xH2O ? Cu(BF4)2?xH2O > Co(BF4) 2?6H2O ? Fe(BF4)2? 6H2O > LiBF4 for reactions with cyclohexene oxide and Zn(BF4)2?xH2O ? Co(BF4) 2?6H2O ? Fe(BF4)2? 6H2O > Cu(BF4)2?xH2O for stilbene oxide, but AgBF4 was ineffective. For reaction of styrene oxide with aniline, the metal tetrafluoroborates exhibited comparable regioselectivity (1:99-7:93) with preferential reaction at the benzylic carbon of the epoxide ring. A reversal of regioselectivity (91:1-69:31) in favor of the reaction at the terminal carbon of the epoxide ring was observed for reaction with morpholine. The regioselectivity was dependent on the electronic and steric factors of the epoxide and the pKa of the amine and independent of amine nucleophilicity. The role of the metal tetrafluoroborates is envisaged as "electrophile nucleophile dual activation" through cooperativity of coordination, charge-charge interaction, and hydrogen-bond formation that rationalizes the catalytic efficiency, substrate reactivity, and regioselectivity. The methodology was used for synthesis of cardiovascular drug metoprolol as racemic and enriched enantiomeric forms.
- Pujala, Brahmam,Rana, Shivani,Chakraborti, Asit K.
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scheme or table
p. 8768 - 8780
(2011/12/04)
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- Thieme chemistry journal awardees-where are they now? bifunctional organocatalysis with N-Formyl-l-proline: A novel approach to epoxide ring opening and sulfide oxidation
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A conceptually distinct approach to the aminolysis of 1,2-epoxides, which involves Lewis base-Br?nsted acid catalysis employing N-formyl-l-proline as an easily accessible bifunctional organocatalyst and water as a solvent is presented. The potential of N-formyl-l-proline as organocatalyst for the sulfide oxidation reaction using aqueous hydrogen peroxide as environmentally benign and readily available oxidant is also demonstrated. Good to high yields are achieved for both reactions. Georg Thieme Verlag Stuttgart ? New York.
- Wei, Shengwei,Stingl, Kerstin A.,Wei?, Katharina M.,Tsogoeva, Svetlana B.
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experimental part
p. 707 - 711
(2010/06/13)
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- Asymmetric ring opening of meso-epoxides with aromatic amines catalyzed by a new proline-based N,N′-dioxide-indium tris(triflate) complex
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The catalytic asymmetric ring opening of meso-epoxides with aromatic amines was achieved using a new proline-based N,N′-dioxide-indium tris(triflate) complex in high yields (up to 99%) with excellent enantioselectivities (up to 99% ee) under mild conditio
- Gao, Bo,Wen, Yuehong,Yang, Zhigang,Huang, Xiao,Liu, Xiaohua,Feng, Xiaoming
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supporting information; experimental part
p. 385 - 390
(2009/04/08)
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- Highly efficient and versatile chemoselective addition of amines to epoxides in water catalyzed by erbium(III) triflate
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Er(OTf)3 is proposed as a highly efficient and reusable catalyst for the opening of epoxides in water with aliphatic as well as aromatic amines leading to the synthesis of β-amino alcohols. The aqueous conditions employed in the present method will make it 'environmentally friendly' and potentially useful for industrial applications.
- Procopio, Antonio,Gaspari, Marco,Nardi, Monica,Oliverio, Manuela,Rosati, Ornelio
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p. 2289 - 2293
(2008/09/18)
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- Zr(DS)4 as an efficient catalyst for the aminolysis of epoxides in water
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Zirconium dodecyl sulfate [Zr(DS)4] is an efficient catalyst for the aminolysis of epoxides in water at pH 5.0. Epoxides and anilines were used and the corresponding β-amino alcohols were isolated in generally high regioselectivity and excellen
- Bonollo, Simona,Fringuelli, Francesco,Pizzo, Ferdinando,Vaccaro, Luigi
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p. 2683 - 2686
(2008/02/12)
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- Chiral recyclable dimeric and polymeric Cr(III) salen complexes catalyzed aminolytic kinetic resolution of trans-aromatic epoxides under microwave irradiation
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Aminolytic kinetic resolution (AKR) of trans-stilbene oxide and trans-β-methyl styrene oxide proceeded smoothly under microwave irradiation using chiral dimeric and polymeric Cr(III) salen complexes as efficient catalysts, giving regio-, diastereo-, and enantioselective anti-β-amino alcohols in high yields (49%) and chiral purity (ee up to 94%) in case of 4-methylaniline within 2 min. The kinetic resolution system is approximately five times faster than traditional oil bath heating at 70°C and 420 times faster than the reaction conducted at room temperature with concomitant recovery of respective chirally enriched epoxides (ee, 92%) in excellent yields (up to 48%). The catalyst 1 worked well in terms of enantioselectivity than the catalyst 2, but both the catalysts were easily recovered and reused five times with the retention of its efficiency.
- Kureshy, Rukhsana I.,Prathap, K. Jeya,Singh, Surendra,Agrawal, Santosh,Khan, Noor-Ul H.,Abdi, Sayed H.R.,Jasra, Raksh V.
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p. 809 - 815
(2013/08/22)
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- Catalytic asymmetric ring opening of meso-epoxides with aromatic amines in water
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(Chemical Equation Presented) An operationally simple and environmentally benign protocol for the catalytic asymmetric ring opening of meso-epoxides with aromatic amines has been developed. The reactions proceeded smoothly in the presence of 1 mol % of Sc
- Azoulay, Stephane,Manabe, Kei,Kobayashi, Shu
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p. 4593 - 4595
(2007/10/03)
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- Crossed pinacol coupling reaction between aldehydes and imines: A rapid access to 1,2-amino alcohols
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In the presence of zinc, boron trifluoride etherate, and methyltrichlorosilane, aldehydes and imines underwent a crossed pinacol coupling reaction to give 1,2-amino alcohols in good to excellent yields.
- Shimizu, Makoto,Iwata, Atsushi,Makino, Hiroaki
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p. 1538 - 1540
(2007/10/03)
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- Zirconium sulfophenyl phosphonate as a heterogeneous catalyst in the preparation of β-amino alcohols from epoxides
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A convenient method for the ring opening of epoxides by aromatic amines, catalysed by zirconium sulfophenyl phosphonate in solvent-free conditions, is described.
- Curini, Massimo,Epifano, Francesco,Marcotullio, Maria Carla,Rosati, Ornelio
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p. 4149 - 4152
(2007/10/03)
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- Carbon-carbon bond fragmentation in aminoalcohol radical cations. Kinetics, thermodynamic correlations, and mechanism
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A detailed study of the kinetics, thermodynamics and mechansim of carbon-carbon bond fragmentation in a series of aminoalcohol radical cations is presented. The compounds that provide the basis for this investigation are derived from the parent structure,
- Burton, Richard D.,Bartberger, Michael D.,Zhang, Yin,Eyler, John R.,Schanze, Kirk S.
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p. 5655 - 5664
(2007/10/03)
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- Naphthalene-catalysed lithiation of phenone imines in the presence of carbonyl compounds: Preparation of 1,2-aminoalcohols
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The lithiation of different phenone imines 1 with an excess of lithium powder and a catalytic amount (8 mol %) of naphthalene in the presence of several carbonyl compounds 2 in tetrahydrofuran at temperatures ranging between -78 and 20°C leads, after hydrolysis with water, to the corresponding 1,2-aminoalcohols 3 in moderate yields.
- Guijarro, David,Yus, Miguel
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p. 7761 - 7768
(2007/10/02)
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- Electroreductive Coupling of Aromatic Imines with Electrophiles in the Presence of Chlorotrimethylsilane
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Electroreduction of aromatic imines in the presence of electrophiles gave the corresponding inter- and intramolecular coupling products when the reaction was carried out with the use of chlorotrimethylsilane (CTMS) as the trapping agent of an anion interm
- Shono, Tatsuya,Kise, Naoki,Kunimi, Nobutaka,Nomura, Ryoji
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p. 2191 - 2194
(2007/10/02)
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- EPR and ENDOR Study of Chiral Nitroxides
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Racemic and achiral alkyl aryl nitroxides were examined at various temperatures.The restricted rotation of the aminoxyl substituents was indicated both by the β-proton coupling constants and by the inequivalence of the aromatic ortho protons.These results
- Stegmann, Hartmut B.,Schaber, Frank-Martin,Schuler, Paul,Scheffler, Klaus
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p. 887 - 891
(2007/10/02)
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- Stereochemistry of Imino-group Reduction. Part 3. The Hydride Reduction of Achiral Benzil Monoimines
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The RR,SS:RS,SR ratio of diastereoisomeric amino-alcohols obtained from the lithium aluminium hydride reduction of the monoimines prepared by reaction of benzil and various aliphatic and aromatic achiral amines has been determined.Stereochemical results a
- Alcaide, Benito,Lopez-Mardomingo, Carmen,Perez-Ossorio, Rafael,Plumet, Joaquin
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p. 1649 - 1654
(2007/10/02)
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- THE STEREOSELECTIVE REDUCTION OF α-AMINODEOXYBENZOIN DERIVATIVES WITH SODIUM BOROHYDRIDE
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Total stereoselectivity is observed in the sodium borohydride reduction of α-aminodeoxybenzoins and their hydrochlorides in various hydroxylic solvents.RS-SR isomer (erythro) was the only aminoalcohol obtained.
- Alcaide, Benito,Escobar, Gerardo,Gonzalez-Simo, Jose L.,Lopez-Mardomingo, Carmen,Perez-Ossorio, Rafael,Plumet, Joaquin
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p. 2033 - 2036
(2007/10/02)
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