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Organocatalysis

ACh cover 24/2003The term organocatalysis describes the acceleration of chemical reactions through the addition of a substoichiometric quantity of an organic compound. The interest in this field has increased spectacularly in the last few years as result of both the novelty of the concept and, more importantly, the fact that the efficiency and selectivity of many organocatalytic reactions meet the standards of established organic reactions. Organocatalytic reactions are becoming powerful tools in the construction of complex molecular skeletons.[1,2]

[1] P. I. Dalko, L. Moisan,
Angew. Chem. 2001, 113, 3840; Angew. Chem. Int. Ed. 2001, 40, 3726
Angew. Chem. 2004, 116, 5248; Angew. Chem. Int. Ed. 2004, 43, 5138.

[2] Special issue of Adv. Synth. Catal. 2004, 346, Nr. 9-10.

Recent Articles

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Novel (−)-β-Pinene-Derived Triazolium Salts: Synthesis and Application in the Asymmetric Stetter Reaction

Novel (−)‐β‐Pinene‐Derived Triazolium Salts: Synthesis and Application in the Asymmetric Stetter Reaction

Dual enantioselective control: Pseudoenantiomeric triazolium salts prepared from a single precursor, (−)-β-pinene, promote opposite enantiofacial selectivity in the intramolecular Stetter reaction to afford the desired products in excellent yields with excellent stereoselectivity.

[Communication]
Zbigniew Rafiński
ChemCatChem, July 21, 2016, DOI: 10.1002/cctc.201600498. Read article

Asymmetric Aminocatalysis in the Synthesis of δ-Lactone Derivatives

Asymmetric Aminocatalysis in the Synthesis of δ‐Lactone Derivatives

Square up! A novel approach to 3,4-dihydrocoumarins utilizing the aminocatalytic, trienamine-mediated cycloaddition reaction between 2,4-dienals and ethyl coumarincarboxylates is presented. The reaction is promoted by a bifunctional aminocatalyst with a hydrogen-bonding squaramide structural unit. As a consequence, the stereochemical outcome is governed through the double hydrogen-bonding interactions between the hydrogen-bonding moiety of the catalyst and the dienophile.

[Communication]
Anna Albrecht, Anna Skrzyńska, Anna Pietrzak, Jan Bojanowski, Łukasz Albrecht
Asian J. Org. Chem., July 19, 2016, DOI: 10.1002/ajoc.201600272. Read article

Organocatalyzed Group Transfer Polymerization

Organocatalyzed Group Transfer Polymerization

Recent progress in the organocatalyzed group transfer polymerization (GTP) developed by our group since 2009 is described, in terms of the livingness of polymerization, end-functionalized polymer synthesis, block copolymer synthesis, star polymer synthesis, and the elucidation of polymerization mechanisms. The aim of this account is to provide our colleagues with a perspicuous overview on organocatalyzed GTP chemistry.

[Personal Account]
Yougen Chen, Toyoji Kakuchi
The Chemical Record, July 18, 2016, DOI: 10.1002/tcr.201600034. Read article

Mass Spectrometric Back Reaction Screening of Quasi-Enantiomeric Products as a Mechanistic Tool

Mass Spectrometric Back Reaction Screening of Quasi‐Enantiomeric Products as a Mechanistic Tool

Observing back and forth: Mass spectrometric back reaction screening of quasi-enantiomeric products may serve as a valuable tool for examining the mechanism of an enantioselective catalytic process. By comparing the results from the forward and back reaction, direct evidence for the involvement of a catalytic intermediate in the enantioselective step can be obtained. The potential of this method is demonstrated for various organocatalytic asymmetric reactions.

[Personal Account]
Patrick G. Isenegger, Andreas Pfaltz
The Chemical Record, July 15, 2016, DOI: 10.1002/tcr.201600072. Read article

Organocatalytic [3+2] Cycloadditions of Barbiturate-Based Olefins with 3-Isothiocyanato Oxindoles: Highly Diastereoselective and Enantioselective Synthesis of Dispirobarbiturates

Organocatalytic [3+2] Cycloadditions of Barbiturate-Based Olefins with 3-Isothiocyanato Oxindoles: Highly Diastereoselective and Enantioselective Synthesis of Dispirobarbiturates

[Full Paper]
Hong-Wu Zhao, Ting Tian, Hai-Liang Pang, Bo Li, Xiao-Qin Chen, Zhao Yang, Wei Meng, Xiu-Qing Song, Yu-Di Zhao, Yue-Yang Liu
Adv. Synth. Catal., July 13, 2016, DOI: 10.1002/adsc.201600270. Read article.

Hydrothiolation of Alkenes and Alkynes Catalyzed by 3,4-Dimethyl-5-vinylthiazolium iodide and Poly(3,4-dimethyl-5-vinylthiazolium) iodide

Hydrothiolation of Alkenes and Alkynes Catalyzed by 3,4‐Dimethyl‐5‐vinylthiazolium iodide and Poly(3,4‐dimethyl‐5‐vinylthiazolium) iodide

Thio, thio, it's off to work we go! Highly selective anti-Markovnikov addition of thiols to unactivated alkenes and alkynes is demonstrated by using 3,4-dimethyl-5-vinylthiazolium iodide or its polymer, poly(3,4-dimethyl-5-vinylthiazolium) iodide, as a complementary catalyst. DFT calculations support a mechanism in which the thiazolium cation stabilizes a thiyl radical and enhances its reaction with unsaturated C−C bonds.

[Communication]
Supill Chun, Junyong Chung, Ji Eun Park, Young Keun Chung
ChemCatChem, July 06, 2016, DOI: 10.1002/cctc.201600363. Read article

Hydrogen-Bonding Catalysis of Tetraalkylammonium Salts in an Aza-Diels–Alder Reaction

Hydrogen‐Bonding Catalysis of Tetraalkylammonium Salts in an Aza‐Diels–Alder Reaction

Under observation: A piperidine-derived tetraalkylammonium salt with a non-coordinating counteranion worked as an effective hydrogen-bonding catalyst in an aza-Diels–Alder reaction of imines and a Danishefsky diene. The hydrogen-bonding interaction between the ammonium salt and an imine was observed as part of a 1H NMR titration study.

[Communication]
Yusuke Kumatabara, Shiho Kaneko, Satoshi Nakata, Seiji Shirakawa, Keiji Maruoka
Chem. Asian J., July 06, 2016, DOI: 10.1002/asia.201600781. Read article

α,β-Unsaturated Aldehydes in the Synthesis of two-heteroatomic Five-membered Heterocyclic Compounds: Recent Progress due to Development of Metal- and Organocatalysis

The ever-increasing interest in the chemistry of azoles is due to their paramount importance in such essential fields as pharmacology, medicine, biology, organic synthesis of fine chemicals, agricultural chemistry, and the chemical industry. This Review summarizes and highlights the methods for the synthesis of five-membered N,N-, N,O-, and N,S-heterocycles based on transformations of 2-alkenals. Over the last 15 years, these reactions, which often differs from the processes involving other α,β-unsaturated carbonyl compounds in methodology and results, are gathering momentum. The multitude of the catalytic and technological novelties discussed in the review, such as asymmetric metal- and organocatalysis, one-pot multicomponent reactions proceeding through domino, cascade, or tandem sequences, and microwave activation, promote the formation of diverse target products, the structures of which becomes clear from the mechanistic schemes given in the review. The mechanisms discussed reflect great advances in the chemo-, regio-, and stereoselectivity of the reactions with participations of 2-alkenals, which allows new azoles and related compounds (imidazoles, pyrazoles, oxazoles, thiazoles and their hydrogenated derivatives) to be synthesized.

[Focus Review]
Natalia Keiko, Nadezhda Vchislo
Asian J. Org. Chem., July 05, 2016, DOI: 10.1002/ajoc.201600227. Read article

Asymmetric Assisted Tandem Catalysis: Hydroamination followed by Asymmetric Friedel–Crafts Reaction from a Single Chiral N,N,N′,N′-Tetradentate Pyridylmethylamine-Based Ligand

Asymmetric Assisted Tandem Catalysis: Hydroamination followed by Asymmetric Friedel–Crafts Reaction from a Single Chiral N,N,N′,N′‐Tetradentate Pyridylmethylamine‐Based Ligand

Relay race: The first example of an asymmetric assisted tandem catalysis protocol that combines a metallocatalyzed alkyne hydroamination reaction with an asymmetric organocatalyzed Friedel–Crafts reaction is reported. The chiral ligand of the metallocatalyst is converted into a chiral organocatalyst by simple HCl addition. Some enantioinduction confirms the relay of the chiral information between the two catalysts.

[Communication]
Alexandre Aillerie, Violeta Rodriguez-Ruiz, Romain Carlino, Flavien Bourdreux, Régis Guillot, Sophie Bezzenine-Lafollée, Richard Gil, Damien Prim, Jérôme Hannedouche
ChemCatChem, July 01, 2016, DOI: 10.1002/cctc.201600604. Read article

N-Heterocyclic Olefins as Robust Organocatalyst for the Chemical Conversion of Carbon Dioxide to Value-Added Chemicals

N‐Heterocyclic Olefins as Robust Organocatalyst for the Chemical Conversion of Carbon Dioxide to Value‐Added Chemicals

NHO limits: N-Heterocyclic olefins (NHOs) activate CO2 for the formation of oxazolidinones from aziridines as well as the N-formylation of amines with polymethylhydrosiloxane (PMHS) or 9-borabicyclo[3.3.1]nonane (9-BBN) as the reducing agent. These transformations proceed under solvent-free and metal-free mild conditions.

[Full Paper]
Vitthal B. Saptal, Bhalchandra M. Bhanage
ChemSusChem, June 30, 2016, DOI: 10.1002/cssc.201600467. Read article

Asymmetric Aldol Reaction with Formaldehyde: a Challenging Process

Asymmetric Aldol Reaction with Formaldehyde: a Challenging Process

The state of the art in asymmetric aldol reactions with formaldehyde is reviewed, highlighting others’ and our developments accomplished for this challenging process. A variety of acyclic and cyclic functionalised products, bearing tertiary and quaternary stereocentres, can be obtained with good-to-high stereocontrol by using metal- and organocatalytic systems under environmentally friendly conditions.

[Personal Account]
Sara Meninno, Alessandra Lattanzi
The Chemical Record, June 22, 2016, DOI: 10.1002/tcr.201600022. Read article

Safe, Selective, and High-Yielding Synthesis of Acryloyl Chloride in a Continuous-Flow System

Safe, Selective, and High‐Yielding Synthesis of Acryloyl Chloride in a Continuous‐Flow System

The fast and the selective: A continuous-flow methodology is developed for the fast and selective synthesis of the otherwise highly unstable acryloyl chloride. The simple continuous-flow setup can be used on a laboratory scale and allows a high throughput (200 g per day). This system is a sustainable method as it enables a reduction in energy and materials consumption because of the efficient mass and heat transfer and the high process selectivity.

[Full Paper]
Marine Movsisyan, Thomas S. A. Heugebaert, Rudy Dams, Christian V. Stevens
ChemSusChem, June 21, 2016, DOI: 10.1002/cssc.201600348. Read article

N-Heterocyclic Carbene-Catalyzed Synthesis of Multi-Substituted Benzenes from Enals and α-Cyano-β-methylenones

N-Heterocyclic Carbene-Catalyzed Synthesis of Multi-Substituted Benzenes from Enals and α-Cyano-β-methylenones

[Communication]
Chun-Lin Zhang, Zhong-Hua Gao, Zhi-Qin Liang, Song Ye
Adv. Synth. Catal., June 20, 2016, DOI: 10.1002/adsc.201600531. Read article.

Enantioselective Vinylogous Organocascade Reactions

Enantioselective Vinylogous Organocascade Reactions

This article critically describes the developments achieved in the field of enantioselective vinylogous organocascade reactions, charting the conceptual advances, and the milestone reactions that have been essential for reaching highly practical levels of synthetic efficiency.

[Personal Account]
Hamish B. Hepburn, Luca Dell'Amico, Paolo Melchiorre
The Chemical Record, June 03, 2016, DOI: 10.1002/tcr.201600030. Read article

Enantioselective Synthesis of Spirooxindole Enols: Regioselective and Asymmetric [3+2] Cyclization of 3-Isothiocyanato Oxindoles with Dibenzylidene Ketones

Enantioselective Synthesis of Spirooxindole Enols: Regioselective and Asymmetric [3+2] Cyclization of 3‐Isothiocyanato Oxindoles with Dibenzylidene Ketones

Good to be picky: On the basis of asymmetric regioselective [3+2] cycloaddition of 3-isothiocyanato oxindoles with dibenzylidene ketones, the corresponding spirooxindole enols could be obtained in high yields with good-to-excellent diastereo- and enantioselectivities.

[Communication]
Dan Du, Yu Jiang, Qin Xu, Xiao-Ge Li, Min Shi
ChemistryOpen, May 25, 2016, DOI: 10.1002/open.201600034. Read article

An Atropisomerically Enforced Phosphoric Acid for Organocatalytic Asymmetric Reactions

An Atropisomerically Enforced Phosphoric Acid for Organocatalytic Asymmetric Reactions

Three atropisomeric phosphoric acids for organocatalysis were obtained by a single Suzuki coupling reaction, and resolved by HPLC. All three catalysts could be used to promote organocatalytic reactions, rendering up to excellent enantioselectivity (98 % ee), confirming the potential of atropisomeric conformational control at the 3,3'-position of the BINOL core to infuence catalyst performance.

[Full Paper]
Luca Bernardi, Giada Bolzoni, Mariafrancesca Fochi, Michele Mancinelli, Andrea Mazzanti
Eur. J. Org. Chem., May 2, 2016, DOI: 10.1002/ejoc.201600296. Read article.

Catalytic Efficiency of Primary β-Amino Alcohols and Their Derivatives in Organocatalysis

Catalytic Efficiency of Primary β-Amino Alcohols and Their Derivatives in Organocatalysis

This review demonstrates the catalytic efficiency of primary β-amino alcohols and their derivatives in organocatalysis. These simple amino alcohols are inexpensive alternatives to other primary amino organocatalysts, being easy to synthesize and air-stable and offering the potential for introduction of different functional groups and alteration of steric sites.

[Microreview]
Ummareddy Venkata Subba Reddy, Madhu Chennapuram, Chigusa Seki, Eunsang Kwon, Yuko Okuyama, Hiroto Nakano
Eur. J. Org. Chem., April 26, 2016, DOI: 10.1002/ejoc.201600164. Read article.

Novel Base-Free Catalytic Wittig Reaction for the Synthesis of Highly Functionalized Alkenes

Novel Base-Free Catalytic Wittig Reaction for the Synthesis of Highly Functionalized Alkenes

Drop the base: A novel catalytic system based on a readily available phosphine oxide precatalyst for base-free catalytic Wittig reactions has been developed (see scheme). Under the optimized reaction conditions, numerous functionalized alkenes were prepared in yields up to 99 % and with good to excellent E/Z selectivities.

[Full Paper]
Marie-Luis Schirmer, Sven Adomeit, Anke Spannenberg, Thomas Werner
Chem. Eur. J., January 13, 2016, DOI: 10.1002/chem.201503744. Read article.

The First Enantioselective Organocatalytic Synthesis of 3-Spiro-α-Alkylidene-γ-Butyrolactone Oxindoles

The First Enantioselective Organocatalytic Synthesis of 3-Spiro-α-Alkylidene-γ-Butyrolactone Oxindoles

An innovative and flexible methodology catalyzed by bifunctional chiral thioureas was developed to react β-nitro oxindoles with aldehydes (see scheme). This approach allows the first enantioselective synthesis of 3-spiro-α-alkylidene-γ-butyrolactone oxindoles 3 with the aim of merging two potentially bioactive structural motifs: the spirooxindole and the α-alkylidene-γ-butyrolactone.

[Full Paper]
Lucia Cerisoli, Marco Lombardo, Claudio Trombini, Arianna Quintavalla
Chem. Eur. J., January 7, 2016, DOI: 10.1002/chem.201504157. Read article.

Chiral Triazoles in Anion-Binding Catalysis: New Entry to Enantioselective Reissert-Type Reactions

Chiral Triazoles in Anion-Binding Catalysis: New Entry to Enantioselective Reissert-Type Reactions

Against the elements: A family of chiral triazoles has been introduced as innovative C-H bond-based hydrogen donors for anion-binding catalysis. Contrary to the believed inefficiency of the low polarized C-H bonds for promoting organocatalysis, these structures proved to be competitive with respect to the more established N-H-type hydrogen donors in enantioselective Reissert-type reactions.

[Full Paper]
Mercedes Zurro, Sören Asmus, Julia Bamberger, Stephan Beckendorf, Olga García Mancheño
Chem. Eur. J., January 7, 2016, DOI: 10.1002/chem.201504094. Read article.

Acetaldehyde: A Small Organic Molecule with Big Impact on Organocatalytic Reactions

Acetaldehyde: A Small Organic Molecule with Big Impact on Organocatalytic Reactions

Utility of acetaldehyde: Acetaldehyde has recently received a great deal of attention as the simplest enolizable carbonyl compound because of its versatile applications in the synthesis of poly(vinyl alcohol), unnatural amino acids, and medicine (see graphic). This Minireview summarizes a methodologically diverse approach to the synthesis of target molecules by outlining a diverse array of reactions such as aldol, Mannich, Michael, and NHC-catalyzed reactions.

[Minireview]
Sun Min Kim, Young Sug Kim, Dong Wan Kim, Ramon Rios, Jung Woon Yang
Chem. Eur. J., December 15, 2015, DOI: 10.1002/chem.201503960. Read article.

The Resurgence of the Highly Ylidic N-Heterocyclic Olefins as a New Class of Organocatalysts

The Resurgence of the Highly Ylidic N-Heterocyclic Olefins as a New Class of Organocatalysts

One carbon better: N-Heterocyclic olefins, the alkylidene derivatives of the prevalent N-heterocyclic carbenes, have recently emerged as efficient promoters for CO2 fixation and polymerization reactions. Their extraordinarily strong Lewis/Brønsted basicity suggests great potential as a new class of organocatalysts for a broad range of reactions in synthetic chemistry.

[Concept]
Reece D. Crocker, Thanh V. Nguyen
Chem. Eur. J., November 26, 2015, DOI: 10.1002/chem.201503575. Read article.

Whither Organic Synthesis?

Whither Organic Synthesis?

[Review]
Douglass F. Taber
Isr. J. Chem., April 15, 2015, DOI: 10.1002/ijch.201500006. Read article

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