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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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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

Asymmetric Desymmetrization via Metal-Free C−F Bond Activation: Synthesis of 3,5-Diaryl-5-fluoromethyloxazolidin-2-ones with Quaternary Carbon Centers

Asymmetric Desymmetrization via Metal‐Free C−F Bond Activation: Synthesis of 3,5‐Diaryl‐5‐fluoromethyloxazolidin‐2‐ones with Quaternary Carbon Centers

ortho Effect: Non-activated Csp3−F bonds can be cleaved selectively in the novel desymmetrization of 1,3-difluorides. The combination of a cinchona alkaloid based chiral ammonium bifluoride catalyst and N,O-bis(trimethylsilyl)acetamide facilitated the efficient, catalyzed asymmetric Csp3−F bond cleavage. The steric ortho effect plays an important role in the asymmetric induction.

[Communication]
Junki Tanaka, Satoru Suzuki, Etsuko Tokunaga, Günter Haufe, Norio Shibata
Angew. Chem. Int. Ed., June 22, 2016, DOI: 10.1002/anie.201603210. 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

Regioselective Organocatalytic Formation of Carbamates from Substituted Cyclic Carbonates

Regioselective Organocatalytic Formation of Carbamates from Substituted Cyclic Carbonates

[Full Paper]
Sergio Sopeña, Victor Laserna, Wusheng Guo, Eddy Martin, Eduardo C. Escudero-Adán, Arjan W. Kleij
Adv. Synth. Catal., June 2, 2016, DOI: 10.1002/adsc.201600290. Read article.

Development of Bifunctional Thiourea Organocatalysts Derived from a Chloramphenicol Base Scaffold and their Use in the Enantioselective Alcoholysis of meso Cyclic Anhydrides

Development of Bifunctional Thiourea Organocatalysts Derived from a Chloramphenicol Base Scaffold and their Use in the Enantioselective Alcoholysis of meso Cyclic Anhydrides

Conversion by inversion: A series of new chloramphenicol-base-derived thiourea organocatalysts is synthesized and applied for the enantioselective alcoholysis of meso-anhydrides. Hemiesters are afforded with excellent enantioselectivities with a low loading of catalysts with a (1S,2R) configuration. Almost no enantioselectivity is achieved with the use of their diastereoisomers, the (1R,2R) catalysts. The utility of this technology is demonstrated by the synthesis of (R)-(−)-baclofen.

[Full Paper]
Lin-Jie Yan, Hai-Feng Wang, Wen-Xue Chen, Yuan Tao, Kai-Jun Jin, Fen-Er Chen
ChemCatChem, June 02, 2016, DOI: 10.1002/cctc.201600228. Read article

Phosphine–Thiourea-Organocatalyzed Asymmetric C−N and C−S Bond Formation Reactions

Phosphine–Thiourea‐Organocatalyzed Asymmetric C−N and C−S Bond Formation Reactions

Phosphine–thiourea-based organocatalysts derived from l-proline efficiently promote C−N and C−S bond formation through the asymmetric allylic substitution of tert-butoxycarbonyloxy-Morita–Baylis–Hillman (MBH) adducts with phthalimide or alkyl thiols, respectively. The desired products are afforded in good yields and enantioselectivities.

[Communication]
Thi-Thuy-Duong Ngo, Thi-Huong Nguyen, Chloée Bournaud, Régis Guillot, Martial Toffano, Giang Vo-Thanh
Asian J. Org. Chem., May 30, 2016, DOI: 10.1002/ajoc.201600212. 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

Direct N-Acylation of Sulfoximines with Aldehydes by N-Heterocyclic Carbene Catalysis under Oxidative Conditions

Direct N‐Acylation of Sulfoximines with Aldehydes by N‐Heterocyclic Carbene Catalysis under Oxidative Conditions

Imines Business: An efficient, catalytic, and scalable method for the direct N-acylation of sulfoximines with readily available N-heterocyclic carbene (NHC)-catalysts and aldehydes that affords various functionalized N-acylsulfoximines in good-to-excellent yields has been developed.

[Communication]
Arka Porey, Surojit Santra, Joyram Guin
Asian J. Org. Chem., May 19, 2016, DOI: 10.1002/ajoc.201600163. Read article

Rational Design of Amine Nucleophiles for Dynamic Kinetic Resolution of Azlactones Leading to Highly Enantioselective Synthesis of Bisamides

Rational Design of Amine Nucleophiles for Dynamic Kinetic Resolution of Azlactones Leading to Highly Enantioselective Synthesis of Bisamides

High-resolution chemistry: The first catalytic asymmetric aminolysis of azlactones was established, enabling the highly enantioselective dynamic kinetic resolution of azlactones, which is an efficient method for synthesizing optically pure bisamides in high yields with excellent enantioselectivities (up to 99 % yield, 99 % ee).

[Full Paper]
Yu-Chen Zhang, Qin Yang, Xue Yang, Qiu-Ning Zhu, Feng Shi
Asian J. Org. Chem., May 11, 2016, DOI: 10.1002/ajoc.201600185. 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.

Imidazolium-Based Poly(Ionic Liquid)s Featuring Acetate Counter Anions: Thermally Latent and Recyclable Precursors of Polymer-Supported N-Heterocyclic Carbenes for Organocatalysis

Imidazolium‐Based Poly(Ionic Liquid)s Featuring Acetate Counter Anions: Thermally Latent and Recyclable Precursors of Polymer‐Supported N‐Heterocyclic Carbenes for Organocatalysis

Statistical styrenic-type copoly(ionic liquid)s based on imidazolium units and featuring weakly basic acetate counter-anions behave as thermally latent and recyclable precursors of polymer-supported N-heterocyclic carbenes for the purpose of organocatalysis.

[Communication]
Romain Lambert, Paul Coupillaud, Anne-Laure Wirotius, Joan Vignolle, Daniel Taton
Macromol. Rapid Commun., March 18, 2016, DOI: 10.1002/marc.201600019. 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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