Highly Enantioselective Aza-Henry Reaction of Ketoimines Catalyzed by Chiral <i>N</i>,<i>N</i>′-Dioxide−Copper(I) Complexes
Organic LettersPublished 28 October 2008
Cheng Tan, Xiaohua Liu, Liwei Wang, Jun Wang, Xiaoming Feng
Citations114
SJR quartileQ1
SJR score1.24
SNIP1.03
Generate an AI Snapshot to get a quick, structured summary of this paper.
Study Snapshot
ObjectiveStudy objective
MethodsResearch methodology
PopulationPopulation studied
Sample sizeSample sizes
OutcomesStudy outcomes here
ResultsStudy results comes here
LimitationsResearch study limitations comes here
A concise AI-generated summary of the paper will appear here once you click Generate AI Snapshot.
TL;DR
The first example of catalytic enantioselective aza-Henry reaction of ketoimines has been realized using a simple chiral N,N'-dioxide-Cu(I) complex as catalyst.
Abstract
The first example of catalytic enantioselective aza-Henry reaction of ketoimines has been realized using a simple chiral N,N'-dioxide-Cu(I) complex as catalyst. It performs well over a range of substrates to give the corresponding products in moderate to good yields (up to 83%) with high enantioselectivities (up to 96% ee).
Keywords
ChemistryPharmacology, Toxicology and Pharmaceutics
Angewandte Chemie International EditionThe Chemistry of Vicinal Diamines
985 Citations1998Denis Lucet, Thierry Le Gall +1 more
Especially in the field of enantioselective synthesis, vicinal diamines (1,2-diamines) 1 and compounds easily prepared from them are widely used by organic chemists and various strategies have been developed to produce these compounds selectively.
SynthesisCatalytic Enantioselective Construction of All-Carbon Quaternary Stereocenters
981 Citations2006Barry M. Trost, Chunhui Jiang
Proceedings of the National Academy of SciencesCatalytic asymmetric synthesis of all-carbon quaternary stereocenters
828 Citations2004Christopher J. Douglas, Larry E. Overman
Chemical ReviewsCatalytic Asymmetric Synthesis of α-Amino Acids
812 Citations2007Carmén Nájera, José M. Sansano
Chemical ReviewsAsymmetric Synthesis of Tertiary Alcohols and α-Tertiary Amines via Cu-Catalyzed C−C Bond Formation to Ketones and Ketimines
612 Citations2008Masakatsu Shibasaki, Motomu Kanai
Asymmetric catalysts that promote C-C bond-formation to ketones and ketimines should have high catalyst activity and enantioselectivity for synthetically more efficient addition to tetrasubstituted carbon synthesis.
European Journal of Organic ChemistryEnantioselective Catalytic Formation of Quaternary Stereogenic Centers
545 Citations2007Pier Giorgio Cozzi, Robert Hilgraf +1 more
Advanced Synthesis & CatalysisStereoselective Construction of Quaternary Stereocenters
517 Citations2005Jens Christoffers, Angelika Baro
TetrahedronRecent developments in asymmetric catalytic addition to CN bonds
461 Citations2006Gregory K. Friestad, Alex K. Mathies
European Journal of Organic ChemistryOrganocatalytic Asymmetric Mannich Reactions: New Methodology, Catalyst Design, and Synthetic Applications
455 Citations2007Amal Ting, Scott E. Schaus
Organic & Biomolecular ChemistryAsymmetric catalysis for the construction of quaternary carbon centres: nucleophilic addition on ketones and ketimines
450 Citations2007Olivier Riant, Jérôme Hannedouche
A view of the literature from this growing area of research will be presented in this review, with an emphasis on the pioneer works and milestones brought by the main players in this field.
TetrahedronRecent synthetic developments in the nitro to carbonyl conversion (Nef reaction)
434 Citations2003Roberto Ballini, Marino Petrini
Organic & Biomolecular ChemistryRecent approaches towards the asymmetric synthesis of α,α-disubstituted α-amino acids
390 Citations2006Henning Vogt, Stefan Bräse
The class of alpha,alpha-disubstituted alpha-amino acids has gained considerable attention in the past decades and continues doing so and has inspired the development of many new methodologies for their asymmetric construction.
Organic LettersEnantioselective Aza-Henry Reaction Catalyzed by a Bifunctional Organocatalyst
375 Citations2004Tomotaka Okino, Satoru Nakamura +2 more
The aza-Henry reaction of imines with nitroalkanes was promoted by chiral thiourea with an N,N-dimethylamino group to give beta-nitroamines with good enantioselectivity.
Journal of the American Chemical SocietyChiral Proton Catalysis: A Catalytic Enantioselective Direct Aza-Henry Reaction
356 Citations2004Benjamin M. Nugent, Ryan A. Yoder +1 more
This discovery suggests the use of ionic hydrogen bonds in asymmetric catalysis may not only be more general than previously thought, but also a viable "green" approach to single-enantiomer organic compounds.
Angewandte Chemie International EditionHighly Enantioselective Thiourea‐Catalyzed Nitro‐Mannich Reactions
309 Citations2004Tehshik P. Yoon, Eric N. Jacobsen
Journal of the American Chemical SocietyA Bench-Stable Homodinuclear Ni<sub>2</sub>−Schiff Base Complex for Catalytic Asymmetric Synthesis of α-Tetrasubstituted <i>anti</i>-α,β-Diamino Acid Surrogates
301 Citations2008Zhihua Chen, Hiroyuki Morimoto +2 more
Catalytic asymmetric direct Mannich-type reactions of α-substituted nitroacetates using a new bench-stable homodinuclear Ni2−Schiff base 1b complex are described, giving products in high stereoselectivity.
European Journal of Organic ChemistryChiral <i>N</i>‐Oxides in Asymmetric Catalysis
274 Citations2006Andrei V. Malkov, Pavel Kočovský
Journal of the American Chemical Society<i>syn</i>-Selective Catalytic Asymmetric Nitro-Mannich Reactions Using a Heterobimetallic Cu−Sm−Schiff Base Complex
236 Citations2007Shinya Handa, Vijay Gnanadesikan +2 more
The present method is complementary to the previously reported methods, and products were obtained in high syn-selectivity (>20:1), yield, yield, and enantioselectivity (98−83% ee).
Journal of the American Chemical SocietyThe First Catalytic Asymmetric Aza-Henry Reaction of Nitronates with Imines: A Novel Approach to Optically Active β-Nitro-α-Amino Acid- and α,β-Diamino Acid Derivatives
227 Citations2001Kristian Rahbek Knudsen, Tine Risgaard +3 more
Tetrahedron AsymmetryChiral pyridine N-oxides: useful ligands for asymmetric catalysis
226 Citations2004Giorgio Chelucci, Gabriele Murineddu +1 more
Angewandte Chemie International EditionThe First Catalytic Asymmetric Nitro-Mannich-Type Reaction Promoted by a New Heterobimetallic Complex
206 Citations1999Ken‐ichi Yamada, Simon J. Harwood +2 more
The best ratio is 1:1:3 for the components Yb, K, and binaphthol in the new heterobimetallic complex, which efficiently catalyzes an asymmetric nitro-Mannich-type reaction.
Angewandte Chemie International EditionAsymmetric Catalytic Aza‐Henry Reactions Leading to 1,2‐Diamines and 1,2‐Diaminocarboxylic Acids
197 Citations2003Bernhard Westermann
Journal of the American Chemical SocietyEnantioselective Aza-Henry Reaction with an <i>N</i>-Sulfinyl Urea Organocatalyst
191 Citations2007MaryAnn T. Robak, Mónica Trincado +1 more
A new class of organocatalyst has been developed that incorporates a sulfinyl group as a urea or thiourea substituent that serves to simultaneously acidify the urea and provide asymmetric induction in hydrogen-bond-catalyzed reactions.
Angewandte Chemie International EditionCatalytic Enantioselective Addition of Nitro Compounds to Imines—A Simple Approach for the Synthesis of Optically Activeβ-Nitro-α-Amino Esters
189 Citations2001Nagatoshi Nishiwaki, Kristian Rahbek Knudsen +2 more
The catalytic and asymmetric nitro-Mannich reaction of nitro compounds to α-imino ester catalyzed by chiral bisoxazoline-copper complexes gave β-nitro-α-amino esters with excellent diastereo- and enantioselectivities.
Journal of the American Chemical SocietyCatalytic Enantioselective Aza-Henry Reaction with Broad Substrate Scope
182 Citations2005Claudio Palomo, Mikel Oiarbide +2 more
This work represents the first general enantioselective aza-Henry method for azomethines derived from enolizable aldehydes, giving rise to enantiomeric excesses above 94%.
Angewandte Chemie International EditionPhase‐Transfer‐Catalyzed Asymmetric Aza‐Henry Reaction Using <i>N</i>‐Carbamoyl Imines Generated In Situ from α‐Amido Sulfones
176 Citations2005Francesco Fini, Valentina Sgarzani +4 more
Chemistry - A European JournalBifunctional‐Thiourea‐Catalyzed Diastereo‐ and Enantioselective Aza‐Henry Reaction
167 Citations2005Xuenong Xu, Tomihiro Furukawa +3 more
Bifunctional thiourea 1a catalyzes aza-Henry reaction of nitroalkanes with N-Boc-imines to give syn-beta-nitroamines with good to high diastereo- and enantioselectivity.
Journal of the American Chemical SocietyChiral Ammonium Betaines: A Bifunctional Organic Base Catalyst for Asymmetric Mannich-Type Reaction of α-Nitrocarboxylates
161 Citations2008Daisuke Uraguchi, Kyohei Koshimoto +1 more
The present study provides a conceptually new approach toward the design of bifunctional, chiral quaternary ammonium salts and their utilizations as a homogeneous organic molecular catalyst.
Journal of the American Chemical SocietyHighly <i>anti</i>-Selective Asymmetric Nitro-Mannich Reactions Catalyzed by Bifunctional Amine-Thiourea-Bearing Multiple Hydrogen-Bonding Donors
158 Citations2008Chun‐Jiang Wang, Xiu‐Qin Dong +3 more
Highly anti-selective and enantioselective nitro-Mannich reactions have been achieved for a broad spectrum of substrates catalyzed by chiral bifunctional multiple hydrogen-bonding-donor amine-thioureas.
Journal of the American Chemical SocietyA Diastereo- and Enantioselective Synthesis of α-Substituted <i>syn</i>-α,β-Diamino Acids
158 Citations2008Anand Singh, Jeffrey N. Johnston
The bifunctional chiral protic acid catalyst enables these reactions to proceed without separate preactivation of either substrate, leading to a straightforward synthetic protocol for the formation of alpha,beta-diamino phenyl alanine derivatives.
The Journal of Organic ChemistryHighly Enantioselective Henry (Nitroaldol) Reaction of Aldehydes and α-Ketoesters Catalyzed by <i>N</i>,<i>N</i>‘-Dioxide-Copper(I) Complexes
155 Citations2007Bo Qin, Xiao Xiao +4 more
A new chiral N,N'-dioxide-Cu(I) catalyst has been developed for the asymmetric Henry (nitroaldol) reaction and the proposed mechanism was presented to explain the origin of reactivity and asymmetric inductivity.
Journal of the American Chemical SocietyAsymmetric Aza-Henry Reaction Under Phase Transfer Catalysis: An Experimental and Theoretical Study
153 Citations2008Enrique Gómez‐Bengoa, Anthony Linden +4 more
An unusual hydrogen bond pattern for the catalyst-nitrocompounds-imine complex is predicted, where the catalyst OH group interacts with the NO2 group of the nitrocompound.
Current Organic ChemistryRecent Advances in Catalytic Asymmetric Addition to Imines and Related C=N Systems
150 Citations2005Tirayut Vilaivan, Worawan Bhanthumnavin +1 more
Journal of the American Chemical SocietyChiral Proton Catalysis: Enantioselective Brønsted Acid Catalyzed Additions of Nitroacetic Acid Derivatives as Glycine Equivalents
146 Citations2007Anand Singh, Ryan A. Yoder +2 more
An unsymmetrical, bifunctional chiral proton catalyst has been developed to enable the highly diastereo- and enantioselective synthesis of epimerizable addition products from nitroacetic acid esters.
TetrahedronEnantioselective aza-Henry reaction using cinchona organocatalysts
139 Citations2005Luca Bernardi, Francesco Fini +3 more
Organic & Biomolecular ChemistryA chiral molecular recognition approach to the formation of optically active quaternary centres in aza-Henry reactions
138 Citations2005Kristian Rahbek Knudsen, Karl Anker Jørgensen
An approach to asymmetric catalysis based on chiral molecular recognition by the combination of chiral Lewis acids and chiral organocatalysis for the formation of optically active quarternary centers in the aza-Henry reaction is presented.
Angewandte Chemie International EditionAn <i>N</i>,<i>N</i>′‐Dioxide/In(OTf)<sub>3</sub> Catalyst for the Asymmetric Hetero‐Diels–Alder Reaction Between Danishefsky's Dienes and Aldehydes: Application in the Total Synthesis of Triketide
138 Citations2008Zhipeng Yu, Xiaohua Liu +3 more
Organic LettersBrønsted-Acid-Catalyzed Activation of Nitroalkanes: A Direct Enantioselective Aza-Henry Reaction
126 Citations2008Magnus Rueping, Andrey P. Antonchick
A direct asymmetric organocatalytic aza-Henry reaction has been developed in which a new bifunctional Brønsted-acid-catalyzed activation of nitroalkanes provides an efficient access to alpha,beta-diamino acids with high dia- and enantioselectivities under mild and base-free reaction conditions.
The Journal of Organic ChemistryThe Nitro-Mannich Reaction and Its Application to the Stereoselective Synthesis of 1,2-Diamines
116 Citations1998Harry Adams, James C. Anderson +2 more
The Journal of Organic ChemistryAn Expedient and Practical Method for the Synthesis of a Diverse Series of Cyclopropane α-Amino Acids and Amines
113 Citations2004Ryan P. Wurz, André B. Charette
A "one-pot" procedure involving sequential cyclopropanation and reduction is described, and the method can also be applied to the preparation of arylcyclopropyl amines.
Angewandte Chemie International EditionEnantioselective Aza‐Henry Reactions Assisted by Zn<sup>II</sup> and <i>N</i>‐Methylephedrine
110 Citations2005Claudio Palomo, Mikel Oiarbide +3 more
Organic LettersDinuclear Zinc-Catalyzed Enantioselective Aza-Henry Reaction
110 Citations2007Barry M. Trost, David W. Lupton
Angewandte Chemie International EditionLewis Acid Catalysis in Water with a Hydrophilic Substrate: Scandium‐Catalyzed Hydroxymethylation with Aqueous Formaldehyde in Water
108 Citations2008Masaya Kokubo, Chikako Ogawa +1 more
A catalytic hydroxymethylation reaction with aqueous formaldehyde in which water is the sole solvent is described and it can be said that despite the good solubility of H CHO in water, the amount of HCHO in the hydrophobic environment increases in the presence of Sc(DS)3.
The Journal of Organic ChemistryEnantioselective Allylation of Ketones Catalyzed by <i>N</i>,<i>N</i>‘-Dioxide and Indium(III) Complex
102 Citations2007Xin Zhang, Donghui Chen +2 more
A possible catalytic cycle including a transition state has been proposed to explain the origin of the reactivity and asymmetric inductivity, and a bifunctional catalyst was described with Lewis base N-oxide activating tetraallyltin and Lewis acid indium activating ketone.
Chemistry - A European JournalDiscovery of Bifunctional Thiourea/Secondary‐Amine Organocatalysts for the Highly Stereoselective Nitro‐Mannich Reaction of α‐Substituted Nitroacetates
97 Citations2008Bo Han, Qing‐Ping Liu +5 more
TetrahedronA general organic catalyst for asymmetric addition of stabilized nucleophiles to acyl imines
96 Citations2006Christiane M. Bode, Amal Ting +1 more
Organic LettersNovel Bifunctional Chiral Thiourea Catalyzed Highly Enantioselective aza-Henry Reaction
95 Citations2008Chungui Wang, Zhenghong Zhou +1 more
A novel bifunctional chiral thiourea organocatalyst bearing a glycosyl scaffold and a tertiary amino group was synthesized starting from readily available alpha-D-glucose and was proven to be an effective organoc atalyst for the asymmetric aza-Henry reaction between N-Boc imines and nitromethane.
SynlettThe First Enantioselective and Diastereoselective Catalytic Nitro-Mannich Reaction: A New Entry to Chiral Vicinal Diamines
94 Citations2001Ken‐ichi Yamada, Guido Moll +1 more
Advanced Synthesis & CatalysisA Novel Bis‐Thiourea Organocatalyst for the Asymmetric Aza‐Henry Reaction
92 Citations2008Constantinos Rampalakos, William D. Wulff
The success of the present catalyst demonstrates the potential of bis-thioureas as an interesting class of relatively unexplored catalysts, and a model is proposed for the catalyst action where the both components of the reaction are activated simultaneously by hydrogen bonding.
The Journal of Organic ChemistryEnantioselective Aza-Diels−Alder Reaction of Aldimines with “Danishefsky-Type Diene” Catalyzed by Chiral Scandium(III)-<i>N</i>,<i>N</i><i>‘</i>-Dioxide Complexes
91 Citations2007Deju Shang, Junguo Xin +4 more
A new kind of complex prepared from scandium(III) triflate and l-proline-derived N,N'-dioxides has been developed to catalyze the enantioselective aza-Diels-Alder reaction between 1,3-butadiene (diene 1) and aldimines 2, affording the corresponding 2,5-disubstituted dihydropyridinones in moderate to high yields.
Organic & Biomolecular ChemistryHighly diastereoselective addition of nitromethane anion to chiral α-amidoalkylphenyl sulfones. Synthesis of optically active α-amino acid derivatives
85 Citations2003Elisabetta Foresti, Gianni Palmieri +2 more
PM3 semiempirical calculations provide a rationale for the observed opposite stereoselectivity of optically active beta-hydroxy-alpha-amino acid and alpha,beta-diamino acid esters in good yield.
The Journal of Organic ChemistryAn Asymmetric Nitro-Mannich Reaction Applicable to Alkyl, Aryl, and Heterocyclic Imines
78 Citations2005James C. Anderson, Gareth P. Howell +2 more
It is shown that the enantioselective nitro-Mannich coupling between alkyl, aryl, and heterocyclic p-methoxybenzylimines and trimethylsilylnitropropanate catalyzed by a chiral tBu-BOX Cu(II) catalyst gives the highest yields and selectivities for a broad substrate range including nonaromatic aldimines.
Angewandte Chemie International EditionHighly Enantioselective Direct Michael Addition of Nitroalkanes to Nitroolefins Catalyzed by La(OTf)<sub>3</sub>/<i>N</i>,<i>N</i>′‐Dioxide Complexes
77 Citations2008Yang Xu, Xin Zhou +4 more
The direct asymmetric Michael addition of unmodifiedNitroalkanes to nitroalkenes is described by using lanthanum(III) triflate in combination with an N,N’-dioxide ligand.
Chemistry - A European JournalDirect Allylation of Aldimines Catalyzed by <i>C</i><sub>2</sub>‐Symmetric <i>N</i>,<i>N′</i>‐Dioxide–Sc<sup>III</sup> Complexes: Highly Enantioselective Synthesis of Homoallylic Amines
73 Citations2008Xing Li, Xiaohua Liu +4 more
An efficient catalytic asymmetric direct allylation of aldimines promoted by readily accessible and tuneable C2-symmetric N,N’-dioxide-Sc III complexes under mild conditions is reported.
The Journal of Organic ChemistryOrganocatalyzed Solvent-Free Aza-Henry Reaction: A Breakthrough in the One-Pot Synthesis of 1,2-Diamines
73 Citations2004Luca Bernardi, Bianca F. Bonini +5 more
A nitrogen-containing superbase such as TMG was found to be an effective catalyst for the reaction between N-diphenylphosphinoyl imines and nitroalkanes, and a three-step, one-pot synthesis of a range of 1,2-diamines is devised, making use of environmentally friendly procedures in the various steps.
TetrahedronHighly efficient one- or two-step sequences for the synthesis of fine chemicals from versatile nitroalkanes
71 Citations2007Roberto Ballini, Alessandro Palmieri +1 more
The Journal of Organic ChemistryHighly Enantioselective Allylation of α-Ketoesters Catalyzed by <i>N</i>,<i>N</i>‘-Dioxide−In(III) Complexes
70 Citations2007Ke Zheng, Bo Qin +2 more
A possible catalytic cycle including a transition state has been proposed to explain the origin of the reactivity and asymmetric inductivity, and a bifunctional catalysis was described with Lewis base N-oxide activating tetraallylstannane and Lewis acid indium activating α-ketoester.
Chemistry LettersCatalytic Asymmetric Syntheses of ICI-199441 and CP-99994 Using Nitro-Mannich Reaction
64 Citations2002Natsuko Tsuritani, Ken‐ichi Yamada +2 more
The Journal of Organic ChemistryHighly Enantioselective Aza-Henry Reaction of <i>N</i>-Tosyl Imines Catalyzed by <i>N,N</i>‘-Dioxide−Cu(I) Complexes
63 Citations2007Hui Zhou, Dan Peng +4 more
The N,N'-dioxide-Cu(I) complexes have been developed to catalyze the addition of nitromethane to N-tosyl aldimines and a catalytic cycle is proposed to explain the origin of reactivity.
Journal of the Chemical Society Perkin Transactions 1Nitro and related groups
62 Citations2002Joseph P. Adams
The Journal of Organic ChemistryScope and Limitations of the Nitro-Mannich Reaction for the Stereoselective Synthesis of 1,2-Diamines
61 Citations2004James C. Anderson, Alexander J. Blake +2 more
Preliminary results have shown that acetic acid can catalyze the reaction of N-OMB-benzylideneamine with nitropropane, used as solvent, to give the thermodynamically more stable syn-beta-nitroamine product.
Advanced Synthesis & CatalysisAsymmetric Ring Opening of <i>meso</i>‐Epoxides with Aromatic Amines Catalyzed by a New Proline‐Based <i>N</i>,<i>N′</i>‐Dioxide‐Indium Tris(triflate) Complex
61 Citations2008Bo Gao, Yuehong Wen +4 more
Tetrahedron AsymmetryHeterogeneous asymmetric nitro-Mannich reaction using a bis(oxazoline) ligand grafted on mesoporous silica
59 Citations2004Anna Lee, Woo‐Sung Kim +3 more
Organic LettersAsymmetric Aza-Henry Reactions from <i>N</i>-<i>p</i>-Tolylsulfinylimines
51 Citations2005José Luis Garcı́a Ruano, M.D.C. Topp +4 more
Tetrahedron LettersAza-Henry reaction of ketimines catalyzed by guanidine and phosphazene bases
48 Citations2007Nirmal K. Pahadi, Hitoshi Ube +1 more
The methodology developed here is a good template for developing the first organocatalytic approach towards the aza-Henry reaction of ketimines.
Advanced Synthesis & CatalysisHighly Enantioselective Allylation of Aromatic α‐Keto Phosphonates Catalyzed by Chiral <i>N,N′‐</i>Dioxide‐Indium(III) Complexes
46 Citations2008Jinglun Huang, Jing Wang +4 more
The ramipril derivative N,N′-dioxide 3g-indium(III) complex was found to be an efficient catalyst for the allylation of the aromatic α-keto phosphonates.
SynlettOxazoline-Thiourea as a Bifunctional Organocatalyst: Enantioselective aza-Henry Reactions
34 Citations2007Yu‐Wei Chang, Jing‐Jun Yang +2 more
ChiralityAsymmetric aza‐Henry reaction of <i>N</i>‐tosyl imine
29 Citations2006Feifeng Gao, Jiang Zhu +3 more
An efficient stereoselective aza-Henry reaction of N-tosyl imine, catalyzed by the coordination of diethylzinc with a chiral semi-aza-crown ligand, with moderate to high ee (up to 83%) is reported.
TetrahedronPreparation of α-amino ketones, β-amino hydroxylamines using asymmetric aza-Henry reactions of N-p-tolylsulfinylimines with nitroethane
28 Citations2006José Luis Garcı́a Ruano, Jesús López-Cantarero +3 more
The Journal of Organic ChemistryAn Efficient Method for the Synthesis of Nitropiperidones
26 Citations2008José Luis Garcı́a Ruano, Teresa de Haro +2 more
A three step efficient strategy for the synthesis of substituted 5-nitropiperidones in high de, employing Michael addition of N-p-tolylsulfinyl beta-nitroamines to alpha,beta-unsaturated esters, hydrolysis of the sulfinyl group, and cyclization of the resulting free amines is developed.