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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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Catalytic Enantioselective Addition of Pyrazol-5-ones to Trisubstituted Nitroalkenes with an N-Sulfinylurea Organocatalyst

Catalytic Enantioselective Addition of Pyrazol-5-ones to Trisubstituted Nitroalkenes with an N-Sulfinylurea Organocatalyst

[Communication]
James P. Phelan, Jonathan A. Ellman
Adv. Synth. Catal., May 3, 2016, DOI: 10.1002/adsc.201600110. Read article.

Trifunctional Squaramide Catalyst for Efficient Enantioselective Henry Reaction Activation

Trifunctional Squaramide Catalyst for Efficient Enantioselective Henry Reaction Activation

[Full Paper]
Juan V. Alegre-Requena, Eugenia Marqués-López, Raquel P. Herrera
Adv. Synth. Catal., May 3, 2016, DOI: 10.1002/adsc.201600046. 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.

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

An active acyl donor intermediate generated in situ from aldehyde by oxidative NHC-catalysis enables direct acylation of NH-sulfoximine leading to the various N-acylsulfoximines in excellent yields. The reaction performed with an inexpensive carbene catalyst and easily accessible bisquinone oxidant. This straightforward transformation demonstrated a broad substrate scope with respect to sulfoximines and aldehydes. Importantly, the method allowed amidation of several unactivated aliphatic aldehydes in good to moderate yields. Preparative synthesis of N-acylsulfoximine (up to > 2 g) was achieved with this simple methodology.

[Communication]
Arka Porey, Surojit Santra, Joyram Guin
Asian J. Org. Chem., May 02, 2016, DOI: 10.1002/ajoc.201600163. Read article

Site-Selective Calcium-Catalyzed/Organocatalyzed Condensation of Propargyl Alcohols Tethered to β-Keto Esters

Site-Selective Calcium-Catalyzed/Organocatalyzed Condensation of Propargyl Alcohols Tethered to β-Keto Esters

The intramolecular reactivity of an ambident nucleophile with an ambident electrophile is controlled so as to give distinct products from a simple precursor. In particular, the sequential calcium-catalyzed/organocatalyzed condensation pathway leads to synthetically useful 3-vinylcyclopentenones.

[Full Paper]
Sara P. Morcillo, Marc Presset, Sébastien Floquet, Vincent Coeffard, Christine Greck, Christophe Bour, Vincent Gandon
Eur. J. Org. Chem., April 28, 2016, DOI: 10.1002/ejoc.201600394. Read article.

Enantioselective Oxetane Ring Opening with Chloride: Unusual Use of Wet Molecular Sieves for the Controlled Release of HCl

Enantioselective Oxetane Ring Opening with Chloride: Unusual Use of Wet Molecular Sieves for the Controlled Release of HCl

The enantioselective ring opening of oxetanes with chloride provides access to a range of highly functionalized three-carbon building blocks. The use of a new catalyst in combination with wet molecular sieves for the controlled release of HCl leads to high enantioselectivities.

[Communication]
Wen Yang, Zhaobin Wang, Jianwei Sun
Angew. Chem. Int. Ed., April 28, 2016, DOI: 10.1002/anie.201601844. Read article

Photocatalytic Reaction of Diazo Compounds with Aldehydes

Photocatalytic Reaction of Diazo Compounds with Aldehydes

[Full Paper]
K. Rybicka-Jasińska, Ł. W. Ciszewski, D. Gryko
Adv. Synth. Catal., April 27, 2016, DOI: 10.1002/adsc.201600084. 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.

Diastereo- and Enantioselective Synthesis of Spiro-Pyrrolidine-Pyrazolones by Squaramide-Catalyzed Cascade Aza-Michael/Michael Reactions

Diastereo- and Enantioselective Synthesis of Spiro-Pyrrolidine-Pyrazolones by Squaramide-Catalyzed Cascade Aza-Michael/Michael Reactions

A squaramide-catalyzed cascade aza-Michael/Michael addition of either tosylaminomethyl enones or enoates to unsaturated pyrazolones was developed. This new method affords spiro-pyrrolidine-pyrazolones in good to excellent yields (up to 98 %) with excellent diastereoselectivities [up to >20:1 diastereomeric ratio (dr)] and high to excellent enantioselectivities (up to 98 % ee).

[Full Paper]
Jun-Hua Li, Hongliang Wen, Lei Liu, Da-Ming Du
Eur. J. Org. Chem., April 24, 2016, DOI: 10.1002/ejoc.201600316. Read article.

Organocatalytic Enantioselective Alkylation of Pyrazol-3-ones with Isatin-Derived Ketimines: Stereocontrolled Construction of Vicinal Tetrasubstituted Stereocenters

Organocatalytic Enantioselective Alkylation of Pyrazol-3-ones with Isatin-Derived Ketimines: Stereocontrolled Construction of Vicinal Tetrasubstituted Stereocenters

[Communication]
Fares Ibrahim Amr, Carlos Vila, Gonzalo Blay, M. Carmen Muñoz, José R. Pedro
Adv. Synth. Catal., April 24, 2016, DOI: 10.1002/adsc.201600036. Read article.

Organocatalytic Enantioselective Assembly of Spirooxindole-naphthopyrans through Tandem Friedel–Crafts Type/Hemiketalization

Organocatalytic Enantioselective Assembly of Spirooxindole‐naphthopyrans through Tandem Friedel–Crafts Type/Hemiketalization

Purely organic: A facile organocatalytic protocol for the construction of spirooxindole encompassing the naphthopyran ring system is employed by using bifunctional thiourea from proline as the catalyst. Various substituents of the oxindole ring and substitutions either at C6- or C7-position of 2-naphthol are well accommodated under the stabilized conditions.

[Full Paper]
Subramaniam Muthusamy, Muthuraj Prakash, Chandrasekaran Ramakrishnan, M. Michael Gromiha, Venkitasamy Kesavan
ChemCatChem, April 21, 2016, DOI: 10.1002/cctc.201600087. Read article

Asymmetric Synthesis of Nature-Inspired Bioactive Spiro Compounds through Organocatalytic Diels–Alder Reactions

Asymmetric Synthesis of Nature‐Inspired Bioactive Spiro Compounds through Organocatalytic Diels–Alder Reactions

I spi with my little tri: An asymmetric organocatalytic arylideneacetone–olefin [4+2] cycloaddition reaction of arylideneacetones and 1,3-indandione with different aldehydes in ambient conditions is described. The reaction yielded optically pure spirotriones, which were further converted into medicinally useful spiromentins by the Suzuki reaction.

[Communication]
Dhevalapally B. Ramachary, Patoju M. Krishna
Asian J. Org. Chem., April 21, 2016, DOI: 10.1002/ajoc.201600145. Read article

Organocatalytic Enantioselective Transfer Hydrogenation of β-Amino Nitroolefins

Organocatalytic Enantioselective Transfer Hydrogenation of β-Amino Nitroolefins

[Communication]
Antonino Ferraro, Luca Bernardi, Mariafrancesca Fochi
Adv. Synth. Catal., April 19, 2016, DOI: 10.1002/adsc.201600061. Read article.

Organocatalytic Enantioselective Synthesis of Pyrazoles Bearing a Quaternary Stereocenter

Organocatalytic Enantioselective Synthesis of Pyrazoles Bearing a Quaternary Stereocenter

Four's a charm: In an efficient one-pot asymmetric synthesis, pyrazoles bearing a chiral quaternary stereocenter are synthesized by enantioselective addition of pyrazolones to isatin-derived ketimines. The reaction is catalyzed by quinine-derived thiourea, and the corresponding acetylated pyrazoles are obtained in high yields and excellent enantioselectivities after in situ treatment with Ac2O/Et3N.

[Communication]
Carlos Vila, Fares Ibrahim Amr, Gonzalo Blay, M. Carmen Muñoz, José R. Pedro
Chem. Asian J., April 15, 2016, DOI: 10.1002/asia.201600325. Read article

From QCA (Quantum Cellular Automata) to Organocatalytic Reactions with Stabilized Carbenium Ions

From QCA (Quantum Cellular Automata) to Organocatalytic Reactions with Stabilized Carbenium Ions

All roads lead…to carbenium ions! Taking advantage of suggestions inserted in Mayr's table of reactivity, we have explored the use and generation of tailored carbenium ions for many purposes. In this account, we will illustrate the advantage in using carbenium ions for developing different research fields, from quantum cellular automata to stereoselective SN1 type reactions.

[Personal Account]
Andrea Gualandi, Luca Mengozzi, Elisabetta Manoni, Pier Giorgio Cozzi
The Chemical Record, April 09, 2016, DOI: 10.1002/tcr.201500299. Read article

One-Pot Synthesis of Polysubstituted Benzenes through a N,N-dimethyl-4-aminopyridine (DMAP)-Catalyzed [4+2] Benzannulation of 1,3-Bis(sulfonyl)butadienes and γ-Substituted Allenoates

One‐Pot Synthesis of Polysubstituted Benzenes through a N,N‐dimethyl‐4‐aminopyridine (DMAP)‐Catalyzed [4+2] Benzannulation of 1,3‐Bis(sulfonyl)butadienes and γ‐Substituted Allenoates

New domino reaction: An efficient synthetic approach for the construction of polysubstituted benzenes through a N,N-dimethyl-4-aminopyridine (DMAP)-catalyzed [4+2] benzannulation of 1,3-bis(sulfonyl)butadienes and γ-substituted allenoates under mild conditions has been developed.

[Communication]
Meijia Chang, Chengzhou Wu, Jie Zheng, You Huang
Chem. Asian J., April 09, 2016, DOI: 10.1002/asia.201600102. Read article

Grafting of Secondary Diolamides onto [P2W15V3O62]9− Generates Hybrid Heteropoly Acids

Grafting of Secondary Diolamides onto [P2W15V3O62]9− Generates Hybrid Heteropoly Acids

The interaction between an organic amide and the inorganic backbone of [P2W15V3O62]9− generates an organo- heteropolyacid that can be used as a Brønsted organocatalyst (see picture; EWG=electron-withdrawing group). Modeling studies and high-field NMR spectroscopy indicate that the active site is on the nitrogen atom.

[Communication]
David Lachkar, Debora Vilona, Elise Dumont, Moreno Lelli, Emmanuel Lacôte
Angew. Chem. Int. Ed., April 08, 2016, DOI: 10.1002/anie.201510954. Read article

Organo- and Organometallic-Catalytic Intramolecular [1,5]-Hydride Transfer/Cyclization Process through C(sp3)–H Bond Activation

Organo‐ and Organometallic‐Catalytic Intramolecular [1,5]‐Hydride Transfer/Cyclization Process through C(sp3)–H Bond Activation

Organocatalysts have been successfully used for C(sp3)–H functionalization reactions including redox-neutral processes. In this account, we present a tentative summary of organo- and organometallic-catalytic internal redox cascade reactions with respect to the mechanism, the reactivity of hydrogen donors and acceptors, and the migration modes of hydrogen.

[Personal Account]
Su Jin Kwon, Dae Young Kim
The Chemical Record, April 07, 2016, DOI: 10.1002/tcr.201600003. Read article

Domino Reactions Based on Combinatorial Bond Transformations in Electron-Deficient Tertiary Enamines

Domino Reactions Based on Combinatorial Bond Transformations in Electron‐Deficient Tertiary Enamines

Electron-deficient tertiary enamines such as N,N-disubstituted enamines and enaminoesters are stable molecules containing multiple reaction sites, and are highly useful building blocks in organic synthesis. Recent advances in domino reactions designed by using combinatorial transformations on the chemical bonds of these enamines are summarized.

[Personal Account]
Jie-Ping Wan, Yong Gao
The Chemical Record, April 05, 2016, DOI: 10.1002/tcr.201500296. Read article

Asymmetric P−C Bond Formation: Diastereoselective Synthesis of Adjacent P,C-Stereogenic Allylic Phosphorus Compounds

Asymmetric P−C Bond Formation: Diastereoselective Synthesis of Adjacent P,C‐Stereogenic Allylic Phosphorus Compounds

New strategy for adjacent P,C-stereogenic phosphorus compounds: A novel catalytic asymmetric P−C bond formation between phosphinates/phosphine oxide and allylic carbonates was developed. This methodology could not only afford a variety of functionalized adjacent P,C-stereogenic phosphorus compounds in high yields with high regio- and diastereoselectivities but also provide an alternative strategy to access enantiomerically enriched (SP)-phosphinates through kinetic resolution.

[Communication]
Peizhong Xie, Lei Guo, Lanlan Xu, Teck-Peng Loh
Chem. Asian J., March 29, 2016, DOI: 10.1002/asia.201600108. 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

Asymmetric Organocatalytic Assembly of Oxindoles Fused with Spiro-3,4-dihydropyrans with Three Contiguous Stereocenters Consisting of Vicinal Quaternary Centers

Asymmetric Organocatalytic Assembly of Oxindoles Fused with Spiro‐3,4‐dihydropyrans with Three Contiguous Stereocenters Consisting of Vicinal Quaternary Centers

The numbers don't lie: Diverse bispiro-3,4-dihydropyrans consisting of oxindole moieties with three contiguous chiral centers and vicinal quaternary stereocenters were synthesized with very good yields of up to 92 % and excellent enantioselectivity of up to 99 % ee by using a proline-derived thiourea organocatalyst.

[Communication]
Manjunatha Vishwanath, Poopathy Vinayagam, V Pratap Reddy Gajulapalli, Venkitasamy Kesavan
Asian J. Org. Chem., March 16, 2016, DOI: 10.1002/ajoc.201600051. 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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