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Open AccessArticle

A Recyclable Thermoresponsive Catalyst for Highly Asymmetric Henry Reactions in Water

by Meng Wang, Yaoyao Zhang, Zifan Jiang, Yanhui Zhong, Xinzheng Qu, Xingling Li, Bo Xiong, Xianxiang Liu and Lei Zhu

Catalysts 2026, 16(2), 132; https://doi.org/10.3390/catal16020132 (registering DOI) - 1 Feb 2026

Abstract

The synthesis of enantiomerically pure chiral β-nitroalcohols is a crucial objective in asymmetric catalysis. In order to efficiently obtain such chiral products, we developed a series of thermoresponsive, oxazoline–copper catalysts (Cu^II-PN_xFe_yO_z) via sequential reversible [...] Read more.

The synthesis of enantiomerically pure chiral β-nitroalcohols is a crucial objective in asymmetric catalysis. In order to efficiently obtain such chiral products, we developed a series of thermoresponsive, oxazoline–copper catalysts (Cu^II-PN_xFe_yO_z) via sequential reversible addition–fragmentation chain transfer (RAFT) polymerization. These catalysts can self-assemble in water into single-chain nanoparticles (SCNPs) with biomimetic behavior, in which intramolecular hydrophobic and metal-coordination interactions generate a confined hydrophobic cavity. Comprehensive characterization by FT-IR, TEM, DLS, CD, CA, and ICP analysis confirmed the nanostructure and composition. When applied to the aqueous-phase asymmetric Henry reaction between nitromethane and 4-nitrobenzaldehyde, the optimal catalyst (2.0 mol%) achieved a quantitative yield (96%) with excellent enantioselectivity (up to 99%) within 12 h. Furthermore, the thermosensitive poly(N-isopropylacrylamide, NIPAAm) block enabled facile catalyst recovery through temperature-induced precipitation above its lower critical solution temperature (LCST). This work presents an efficient and recyclable biomimetic catalytic system, offering a novel strategy for designing sustainable chiral catalysts for green organic synthesis. Full article

(This article belongs to the Special Issue Catalysis in Polymerizations)

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8 pages, 942 KB

Open AccessCommunication

Highly Effective Asymmetric Henry Reaction Catalyzed by Chiral Complex of Cu (II)-Aziridine-Functionalized Organophosphorus Compounds

by Michał Rachwalski, Julia Wojtaszek, Julia Szymańska and Adam M. Pieczonka

Catalysts 2025, 15(2), 179; https://doi.org/10.3390/catal15020179 - 14 Feb 2025

Cited by 1 | Viewed by 1468

Abstract

A synthesis of organophosphorus compounds containing an aziridine ring, previously described by our group, has been performed and the catalytic activity of the aforementioned chiral heterorganic compounds has been investigated in the asymmetric nitroaldol (Henry) reaction between aromatic/aliphatic aldehydes and nitromethane in the [...] Read more.

A synthesis of organophosphorus compounds containing an aziridine ring, previously described by our group, has been performed and the catalytic activity of the aforementioned chiral heterorganic compounds has been investigated in the asymmetric nitroaldol (Henry) reaction between aromatic/aliphatic aldehydes and nitromethane in the presence of catalytic amounts of copper (II) acetate. In several cases, the chiral β-nitroalcohols have been obtained with high chemical yields and exhibited very high enantiomeric excess values (over 95%). Notably, the use of two enantiomerically pure catalysts, differing in the absolute configuration of the aziridine unit, resulted in the formation of two enantiomeric products of the Henry reaction. Full article

(This article belongs to the Special Issue Catalysis in Heterocyclic and Organometallic Synthesis, 3rd Edition)

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14 pages, 2005 KB

Open AccessArticle

Selectivity Control in Nitroaldol (Henry) Reaction by Changing the Basic Anion in a Chiral Copper(II) Complex Based on (S)-2-Aminomethylpyrrolidine and 3,5-Di-tert-butylsalicylaldehyde

by Olga V. Khromova, Lidiya V. Yashkina, Nadezhda V. Stoletova, Victor I. Maleev, Yuri N. Belokon and Vladimir A. Larionov

Molecules 2024, 29(21), 5207; https://doi.org/10.3390/molecules29215207 - 4 Nov 2024

Cited by 3 | Viewed by 2975

Abstract

This article is a continuation of our previous research on the catalytic capability of a chiral copper complex based on commercially available (S)-2-aminomethylpyrrolidine and 3,5-di-tert-butylsalicylaldehyde with various counter-anions in the asymmetric Henry reaction. Our findings indicate that depending on [...] Read more.

This article is a continuation of our previous research on the catalytic capability of a chiral copper complex based on commercially available (S)-2-aminomethylpyrrolidine and 3,5-di-tert-butylsalicylaldehyde with various counter-anions in the asymmetric Henry reaction. Our findings indicate that depending on the type of base used, chiral nitroalcohols with yields up to 98% and ee values up to 77%, as well as β-nitrostyrenes with yields up to 88%, can be produced. Additionally, it has been found that the outcome of the reaction and the catalytic properties of copper (II) complexes (S)-Cu1 and (S)-Cu2 are influenced by the structure of the aldehyde used. Full article

(This article belongs to the Special Issue Metal-Catalyzed Organic Transformations: Expanding Horizons in Synthetic Methodology)

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16 pages, 2394 KB

Open AccessArticle

Asymmetric Henry Reaction Using Cobalt Complexes with Bisoxazoline Ligands Bearing Two Fluorous Tags

by Kazuki Ishihara, Yamato Kato, Narisa Takeuchi, Yuka Hayashi, Yuna Hagiwara, Shyota Shibuya, Tohya Natsume and Masato Matsugi

Molecules 2023, 28(22), 7632; https://doi.org/10.3390/molecules28227632 - 16 Nov 2023

Cited by 4 | Viewed by 2055

Abstract

The effect of the presence of fluorous tags in bisoxazoline ligands on the stereoselectivity of the cobalt-catalyzed asymmetric Henry reaction was investigated. In contrast to the stereoselectivity obtained with conventional nonfluorous ligands, using bisoxazoline bidentate ligands featuring two fluorous tags in adjacent positions [...] Read more.

The effect of the presence of fluorous tags in bisoxazoline ligands on the stereoselectivity of the cobalt-catalyzed asymmetric Henry reaction was investigated. In contrast to the stereoselectivity obtained with conventional nonfluorous ligands, using bisoxazoline bidentate ligands featuring two fluorous tags in adjacent positions on the aromatic ring yielded a reversed stereoselectivity. The stereoselectivity also reversed when the fluorous tags were replaced with alkyl chains of equivalent length, albeit to a considerably lesser degree, highlighting the effect of the fluorous tags. Full article

(This article belongs to the Special Issue Organic Ligands: Design, Synthesis and Application)

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16 pages, 2948 KB

Open AccessArticle

Asymmetric Henry Reaction of Nitromethane with Substituted Aldehydes Catalyzed by Novel In Situ Generated Chiral Bis(β-Amino Alcohol-Cu(OAc)₂·H₂O Complex

by Abdullah Saleh Alammari, Abdullah Mohammed Al-Majid, Assem Barakat, Saeed Alshahrani, Mohammad Ali and Mohammad Shahidul Islam

Catalysts 2021, 11(10), 1208; https://doi.org/10.3390/catal11101208 - 8 Oct 2021

Cited by 12 | Viewed by 6288

Abstract

Novel chiral thiophene-2,5-bis(β-amino alcohol) ligands (L1–L5) were designed and synthesized from thiophene-2,5-dicarbaldehyde (3) with chiral β-amino alcohols (4a–e) in 4 steps with overall 23% yields. An in situ generated L-Cu(OAc)₂·H₂O [...] Read more.

Novel chiral thiophene-2,5-bis(β-amino alcohol) ligands (L1–L5) were designed and synthesized from thiophene-2,5-dicarbaldehyde (3) with chiral β-amino alcohols (4a–e) in 4 steps with overall 23% yields. An in situ generated L-Cu(OAc)₂·H₂O catalyst system was found to be highly capable catalyst for the asymmetric Henry reaction of nitromethane (7) with various substituted aromatic aldehydes (6a–m) producing chiral nitroaldols product (8a–m) with excellent enantiomeric purity (up to 94.6% ee) and up to >99% chemical yields. 20 mol% of L4-Cu(OAc)₂ catalyst complex in EtOH was effective for the asymmetric Henry transformation in 24 h, at ambient temperature. Ease of ligand synthesis, use of green solvent, base free reaction, mild reaction conditions, high yields and excellent enantioselectivity are all key factors that make this catalytic system robust and highly desirable for the access of versatile building block β-nitro alcohol in practical catalytic usage via asymmetric Henry reaction. Full article

(This article belongs to the Section Catalysis in Organic and Polymer Chemistry)

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12 pages, 770 KB

Open AccessArticle

Heterogeneous Synergistic Catalysis for Promoting Aza-Michael–Henry Tandem Reaction for the Synthesis of Chiral 3-Nitro-1,2-Dihydroquinoline

by Zhe An, Lifeng Chen, Yitao Jiang and Jing He

Catalysts 2019, 9(9), 713; https://doi.org/10.3390/catal9090713 - 24 Aug 2019

Cited by 4 | Viewed by 4302

Abstract

Heterogeneous synergistic catalysis by SBA-15 immobilized chiral amines catalysts has promoted efficient aza-Michael–Henry tandem reaction for the synthesis of chiral 3-Nitro-1,2-Dihydroquinoline. Final products in the asymmetric aza-Michael–Henry cascade reactions between 2-aminobenzaldehyde and β-nitrostyrolene were afforded in a yield of 85% and an enantiomeric [...] Read more.

Heterogeneous synergistic catalysis by SBA-15 immobilized chiral amines catalysts has promoted efficient aza-Michael–Henry tandem reaction for the synthesis of chiral 3-Nitro-1,2-Dihydroquinoline. Final products in the asymmetric aza-Michael–Henry cascade reactions between 2-aminobenzaldehyde and β-nitrostyrolene were afforded in a yield of 85% and an enantiomeric excess (ee) value of 98% on (S)-(–)-2-aminomethyl-1-ethylpyrrolidine immobilized SBA-15. SBA-15-AEP catalyst has been also extended to the asymmetric aza-Michael–Henry cascade reaction of substituted R1-2-aminobenzaldehyde and R2-substituted nitroolefin. The heterogeneous synergistic mechanism for both tertiary amine and secondary amine immobilized mesoporous has been proposed in detail including the geometrical constraints in the ee promotion. Full article

(This article belongs to the Special Issue SBA-15 and Catalysis)

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10 pages, 1939 KB

Open AccessArticle

Asymmetric Henry Reaction of 2-Acylpyridine N-Oxides Catalyzed by a Ni-Aminophenol Sulfonamide Complex: An Unexpected Mononuclear Catalyst

by Mouxiong Liu, Dongdong Gui, Ping Deng and Hui Zhou

Molecules 2019, 24(8), 1471; https://doi.org/10.3390/molecules24081471 - 14 Apr 2019

Cited by 4 | Viewed by 3585

Abstract

The asymmetric Henry reaction of 2-acylpyridine N-oxide remains a challenge as N-oxides generally act as competitive catalyst inhibitors or displace activating ligands. A novel variable yield (up to 99%) asymmetric Henry reaction of 2-acypyridine N-oxides catalyzed by a Ni-aminophenol sulfonamide [...] Read more.

The asymmetric Henry reaction of 2-acylpyridine N-oxide remains a challenge as N-oxides generally act as competitive catalyst inhibitors or displace activating ligands. A novel variable yield (up to 99%) asymmetric Henry reaction of 2-acypyridine N-oxides catalyzed by a Ni-aminophenol sulfonamide complex with good to excellent enantioselectivity (up to 99%) has been developed. Mechanistic studies suggest that the unique properties of the electron-pairs of N-oxides for complexation with Ni makes the unexpected mononuclear complex, rather than the previously reported dinuclear complex, the active species. Full article

(This article belongs to the Special Issue Development of Asymmetric Synthesis)

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11 pages, 1684 KB

Open AccessCommunication

Synthesis and Organocatalytic Asymmetric Nitro-aldol Initiated Cascade Reactions of 2-Acylbenzonitriles Leading to 3,3-Disubstituted Isoindolinones

by Fabio Romano, Antonia Di Mola, Laura Palombi, Maximilian Tiffner, Mario Waser and Antonio Massa

Catalysts 2019, 9(4), 327; https://doi.org/10.3390/catal9040327 - 2 Apr 2019

Cited by 14 | Viewed by 5155

Abstract

In this work, we investigated two strategies for the synthesis of the challenging ketones 2-acylbenzonitriles and we report their use as electrophiles in asymmetric organocatalytic cascade reactions with nitromethane. Promising results were obtained in the presence of chiral bifunctional ammonium salts under phase [...] Read more.

In this work, we investigated two strategies for the synthesis of the challenging ketones 2-acylbenzonitriles and we report their use as electrophiles in asymmetric organocatalytic cascade reactions with nitromethane. Promising results were obtained in the presence of chiral bifunctional ammonium salts under phase transfer conditions, which led to novel 3,3-disubstituted isoindolinones in quantitative yields and moderate enantioselectivity. Full article

(This article belongs to the Special Issue Catalysts for Henry Reaction)

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14 pages, 1742 KB

Open AccessCommunication

Organocatalytic, Asymmetric [2+2+2] Annulation to Construct Six-Membered Spirocyclic Oxindoles with Six Continuous Stereogenic Centers

by Zhi-Long Li, Chao Liu, Rui Tan, Zhi-Ping Tong and Yan-Kai Liu

Catalysts 2016, 6(5), 65; https://doi.org/10.3390/catal6050065 - 27 Apr 2016

Cited by 23 | Viewed by 5490

Abstract

Lactols and cyclic hemiaminals were directly used in a one-pot organo/organo dual catalytic system induced [2+2+2] tandem reaction for the asymmetric construction of six-membered carbocycles. The enamine-based stereoselective Michael addition of lactols or cyclic hemiaminals to electron-deficient olefinic oxindole motifs provided chiral C4 [...] Read more.

Lactols and cyclic hemiaminals were directly used in a one-pot organo/organo dual catalytic system induced [2+2+2] tandem reaction for the asymmetric construction of six-membered carbocycles. The enamine-based stereoselective Michael addition of lactols or cyclic hemiaminals to electron-deficient olefinic oxindole motifs provided chiral C4 components, which were further combined with triethylamine catalyzed Michael/Henry sequential reactions affording spirocyclic oxindole derivatives containing six continuous stereogenic centers with excellent enantioselectivities as a single diastereoisomer. All these desired products have versatile molecular complexity, which might have potential applications in synthetic organic chemistry and the pharmaceutical industry. Full article

(This article belongs to the Special Issue Metal-free Organocatalysis)

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13 pages, 757 KB

Open AccessArticle

Cu (II)-Catalyzed Asymmetric Henry Reaction with a Novel C₁-Symmetric Aminopinane-Derived Ligand

by Liudmila Filippova, Yngve Stenstrøm and Trond Vidar Hansen

Molecules 2015, 20(4), 6224-6236; https://doi.org/10.3390/molecules20046224 - 9 Apr 2015

Cited by 19 | Viewed by 7158

Abstract

A novel C₁-symmetric dinitrogen ligand was synthesized in high yield from commercially available (1R,2R,3R,5S)-(−)-isopinocampheylamine and 1-methyl-2-imidazolecarboxaldehyde. In combination with Cu(OAc)₂H₂O, this new ligand promote the reaction between nitromethane and [...] Read more.

A novel C₁-symmetric dinitrogen ligand was synthesized in high yield from commercially available (1R,2R,3R,5S)-(−)-isopinocampheylamine and 1-methyl-2-imidazolecarboxaldehyde. In combination with Cu(OAc)₂H₂O, this new ligand promote the reaction between nitromethane and aliphatic aldehydes with high yields (up to 97%) and moderate enantioselectivities (up to 67% ee). The reactions with benzaldehyde required prolonged reaction time that resulted in diminished yields, but accompanied with ee-values in the 55%–76% range. Full article

(This article belongs to the Section Organic Chemistry)

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11 pages, 158 KB

Open AccessArticle

Catalytic Asymmetric Nitro-Mannich Reactions with a Yb/K Heterobimetallic Catalyst

by Tatsuya Nitabaru, Naoya Kumagai and Masakatsu Shibasaki

Molecules 2010, 15(3), 1280-1290; https://doi.org/10.3390/molecules15031280 - 4 Mar 2010

Cited by 24 | Viewed by 9557

Abstract

A catalytic asymmetric nitro-Mannich (aza-Henry) reaction with rare earth metal/alkali metal heterobimetallic catalysts is described. A Yb/K heterobimetallic catalyst assembled by an amide-based ligand promoted the asymmetric nitro-Mannich reaction to afford enantioenriched anti-b-nitroamines in up to 86% ee. Facile reduction of the [...] Read more.

A catalytic asymmetric nitro-Mannich (aza-Henry) reaction with rare earth metal/alkali metal heterobimetallic catalysts is described. A Yb/K heterobimetallic catalyst assembled by an amide-based ligand promoted the asymmetric nitro-Mannich reaction to afford enantioenriched anti-b-nitroamines in up to 86% ee. Facile reduction of the nitro functionality allowed for efficient access to optically active 1,2-diamines. Full article

(This article belongs to the Special Issue Bifunctional Catalysis)

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