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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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Xiaoming Shen, Yongtao Wang, Tiandi Wu, Zhenjun Mao, Xufeng Lin
Triply Hydrogen-Bond-Directed Enantioselective Assembly of Pyrrolobenzo-1,4-diazine Skeletons with Quaternary Stereocenters [Communication]

Triply Hydrogen-Bond-Directed Enantioselective Assembly of Pyrrolobenzo-1,4-diazine Skeletons with Quaternary Stereocenters

Tales of the unexpected: An efficient triply hydrogen-bond-directed enantioselective assembly of pyrrolobenzo-1,4-diazine skeletons with quaternary stereocenters by chiral Brønsted acid-catalyzed Pictet–Spengler reaction has been developed. Theoretical calculations reveal that the chiral phosphoric acid catalyst employs unexpected arene C-H···N hydrogen bonding for activation and stereoinduction. SPA=spirocyclic phosphoric acid.

Chem. Eur. J., May 12, 2015, DOI: 10.1002/chem.201500823

Yujiro Hayashi, Shoya Watanabe, Yusuke Yasui, Shigenobu Umemiya
Asymmetric Aldol Reaction of Chloral Catalyzed by Diarylprolinol [Communication]

Asymmetric Aldol Reaction of Chloral Catalyzed by Diarylprolinol

Getting in the pro-zone with pronucleophiles: The asymmetric cross-aldol reaction of chloral hydrate with aldehyde pronucleophiles catalyzed by a CF3-substituted diarylprolinol is accomplished to afford γ-trichloro-β-hydroxy aldehydes in good yields with excellent enantioselectivities. The resulting aldehyde products can be converted into chiral α-azido, α-(4-methyl)phenoxy, and α-fluoro esters without a loss in the diastereo- or enantioselectivities. Bn=benzyl.

ChemCatChem, May 12, 2015, DOI: 10.1002/cctc.201500282

Radell Echemendía, Alexander F. de La Torre, Julia L. Monteiro, Michel Pila, Arlene G. Corrêa, Bernhard Westermann, Daniel G. Rivera, Márcio W. Paixão
Highly Stereoselective Synthesis of Natural-Product-Like Hybrids by an Organocatalytic/Multicomponent Reaction Sequence [Communication]

Highly Stereoselective Synthesis of Natural-Product-Like Hybrids by an Organocatalytic/Multicomponent Reaction Sequence

One shot complexity: The combination of an organocatalytic conjugate addition with a stereoselective multicomponent reaction (MCR) enables the one-pot synthesis of enantiomerically pure natural product hybrids. Such interplay between organocatalysis and MCRs allows the tunable diversification of up to four structural elements, thus facilitating the rapid exploration of a large chemical space.

Angew. Chem. Int. Ed., May 12, 2015, DOI: 10.1002/anie.201412074

Kengo Akagawa, Midori Akiyama, Kazuaki Kudo
Peptide-Catalyzed Desymmetrization of an Achiral Ferrocenyl Compound To Induce Planar Chirality [Short Communication]

Peptide-Catalyzed Desymmetrization of an Achiral Ferrocenyl Compound To Induce Planar Chirality

Planar chirality was induced on an achiral ferrocenyl compound by peptide-catalyzed desymmetrization. Although such an asymmetric reaction could not be realized with a low-molecular-weight catalyst, a resin-supported peptide with a turn structure afforded products in a highly enantioselective manner.

Eur. J. Org. Chem., May 11, 2015, DOI: 10.1002/ejoc.201500428

Nicoletta Brindani, Gloria Rassu, Luca Dell'Amico, Vincenzo Zambrano, Luigi Pinna, Claudio Curti, Andrea Sartori, Lucia Battistini, Giovanni Casiraghi, Giorgio Pelosi, Daniela Greco, Franca Zanardi
Organocatalytic, Asymmetric Eliminative [4+2] Cycloaddition of Allylidene Malononitriles with Enals: Rapid Entry to Cyclohexadiene-Embedding Linear and Angular Polycycles [Communication]

Organocatalytic, Asymmetric Eliminative [4+2] Cycloaddition of Allylidene Malononitriles with Enals: Rapid Entry to Cyclohexadiene-Embedding Linear and Angular Polycycles

Without a trace: The covalent activation of α,β-unsaturated aldehydes with malononitrile produced remotely enolizable π-extended allylidene malononitriles. Their amine-catalyzed eliminative [4+2] cycloaddition to aromatic and aliphatic enals enabled the construction of cyclohexadiene-containing polycycles with outstanding diastereo- and enantioselectivities. The essential role of the malononitrile handle as a traceless activating moiety was demonstrated.

Angew. Chem. Int. Ed., May 7, 2015, DOI: 10.1002/anie.201501894

Michael Addition Catalyzed by Chiral Secondary Amine Phosphoramide Using Fluorinated Silyl Enol Ethers: Formation of Quaternary Carbon Stereocenters

Four C's: The chiral secondary amine phosphoramide A was developed and serves as a powerful catalyst for the Michael addition of fluorinated enol silyl ethers to tetrasubstituted olefins. The resulting products are obtained with high enantioselectivities and contain a quaternary carbon stereocenter bearing either a difluoroalkyl or monofluoroalkyl group. TMS=trimethylsilyl.

Angew. Chem. Int. Ed., May 7, 2015, DOI: 10.1002/anie.201501747

Dominika J. Walaszek, Katarzyna Rybicka-Jasińska, Sabina Smoleń, Maksymilian Karczewski, Dorota Gryko
Mechanistic Insights into Enantioselective C-H Photooxygenation of Aldehydes via Enamine Catalysis [Full Paper]

Vincent Barbier, François Couty, Olivier R. P. David
Morita–Baylis–Hillman Reactions with Nitroalkenes: A Case Study [Full Paper]

Morita–Baylis–Hillman Reactions with Nitroalkenes: A Case Study

Super-nucleophilic pyridine catalysts were used to probe elementary steps of a particular reaction. As a consequence Morita–Baylis–Hillman reactions that employ nitroalkenes can now be performed with great efficiency through catalysis with remarkably low amounts of super-DMAP.

Eur. J. Org. Chem., May 6, 2015, DOI: 10.1002/ejoc.201500207

Shin A. Moteki, Hiroki Maruyama, Keiji Nakayama, Hai-Bei Li, Galina Petrova, Satoshi Maeda, Keiji Morokuma, Keiji Maruoka
Positive Effect of Water in Asymmetric Direct Aldol Reactions with Primary Amine Organocatalyst: Experimental and Computational Studies [Communication]

Positive Effect of Water in Asymmetric Direct Aldol Reactions with Primary Amine Organocatalyst: Experimental and Computational Studies

Primary research: The origin of higher reactivity in the water-accelerated asymmetric aldol reactions with our designed primary amine organocatalyst was elucidated by both computational and experimental methods.

Chem. Asian J., May 5, 2015, DOI: 10.1002/asia.201500078

Florian Bächle, Ivana Fleischer, Andreas Pfaltz
Mass Spectrometric Screening of Racemic Amine Catalysts for Enantioselective Michael Additions [Full Paper]

Yiyong Huang, Xing Yang, Zongchao Lv, Chen Cai, Cheng Kai, Yong Pei, Yu Feng
Asymmetric Synthesis of 1,3-Butadienyl-2-carbinols by the Homoallenylboration of Aldehydes with a Chiral Phosphoric Acid Catalyst [Communication]

Asymmetric Synthesis of 1,3-Butadienyl-2-carbinols by the Homoallenylboration of Aldehydes with a Chiral Phosphoric Acid Catalyst

That important first step: The ability of chiral phosphoric acids to interact simultaneously with a 2,3-dienylboronic ester and an aldehyde through hydrogen bonding enabled enantiospecific C(sp)-C(sp2) bond formation to give versatile synthetic intermediates. A chiral alkyl butadienyl adduct formed in this way on a gram scale was transformed into an optically pure benzo-fused spirocyclic cyclopentenone derivative (see scheme).

Angew. Chem. Int. Ed., May 4, 2015, DOI: 10.1002/anie.201501832

Adrian Ortiz, Tamas Benkovics, Gregory L. Beutner, Zhongping Shi, Michael Bultman, Jeffrey Nye, Chris Sfouggatakis, David R. Kronenthal
Scalable Synthesis of the Potent HIV Inhibitor BMS-986001 by Non-Enzymatic Dynamic Kinetic Asymmetric Transformation (DYKAT) [Communication]

Scalable Synthesis of the Potent HIV Inhibitor BMS-986001 by Non-Enzymatic Dynamic Kinetic Asymmetric Transformation (DYKAT)

Good dynamic: Described is the synthesis of BMS-986001 by employing two novel organocatalytic transformations: a highly selective pyranose to furanose ring tautomerization, and an unprecedented small-molecule-mediated dynamic kinetic asymmetric transformation (DYKAT) to access enantiopure pyranones. BMS-986001 was synthesized in five steps in an overall yield of 44 %. Bz=benzoyl.

Angew. Chem. Int. Ed., April 29, 2015, DOI: 10.1002/anie.201502290

Zhuo Xin, Camille Lescot, Stig D. Friis, Kim Daasbjerg, Troels Skrydstrup
Organocatalyzed CO2 Trapping Using Alkynyl Indoles [Communication]

Organocatalyzed CO2 Trapping Using Alkynyl Indoles

Caught in a trap: The first trapping of CO2 through organocatalyzed C-C and C-O bond formation is reported. By using alkynyl indoles, this method generates novel indole lactone derivatives by using as little as 5 mol % of the simple organic base 1,5,7-triazabicyclo-[4.4.0]dec-5-ene as an organocatalyst. The transformation shows excellent atom economy and a broad substrate scope, including aromatic, heteroaromatic, and aliphatic 2-alkynyl indoles.

Angew. Chem. Int. Ed., April 23, 2015, DOI: 10.1002/anie.201500233

Design, Synthesis, and Application of a Chiral Sulfinamide Phosphine Catalyst for the Enantioselective Intramolecular Rauhut–Currier Reaction

Xiao-Phos: A new class of chiral sulfinamide phosphine catalyst was developed. These Xiao-Phos catalysts can be prepared from inexpensive commercially available starting materials and show good performance in the enantioselective intramolecular Rauhut–Currier reaction under mild conditions. Moreover, kinetic resolution was also observed with the use of two different substituted racemic precursors.

Angew. Chem. Int. Ed., April 23, 2015, DOI: 10.1002/anie.201500907

Christopher J. Collett, Richard S. Massey, James E. Taylor, Oliver R. Maguire, AnnMarie C. O'Donoghue, Andrew D. Smith
Rate and Equilibrium Constants for the Addition of N-Heterocyclic Carbenes into Benzaldehydes: A Remarkable 2-Substituent Effect [Communication]

Rate and Equilibrium Constants for the Addition of N-Heterocyclic Carbenes into Benzaldehydes: A Remarkable 2-Substituent Effect

It takes 2-: Measurement of rate and equilibrium constants for the reaction between N-aryl triazolium NHC precatalysts and substituted benzaldehydes under catalytic and stoichiometric conditions demonstrate the remarkable kinetic and thermodynamic effect of the benzaldehyde 2-substituent in these reactions, potentially providing insight into the chemoselectivity of cross-benzoin reactions.

Angew. Chem. Int. Ed., April 23, 2015, DOI: 10.1002/anie.201501840

Julen Etxabe, Joseba Izquierdo, Aitor Landa, Mikel Oiarbide, Claudio Palomo
Catalytic Enantioselective Synthesis of N,Cα,Cα-Trisubstituted α-Amino Acid Derivatives Using 1H-Imidazol-4(5H)-ones as Key Templates [Communication]

Catalytic Enantioselective Synthesis of N,Cα,Cα-Trisubstituted α-Amino Acid Derivatives Using 1H-Imidazol-4(5H)-ones as Key Templates

A BB method: 1H-imidazol-4(5H)-ones serve as effective and easily available α-amino acid surrogates for the catalytic and highly diastereo- and enantioselective direct construction of N-substituted quaternary α-amino acid derivatives. The reaction is catalyzed by a Brønsted base (BB) and proceeds with different Michael acceptors. EWG=electron-withdrawing group.

Angew. Chem. Int. Ed., April 23, 2015, DOI: 10.1002/anie.201501275

Douglass F. Taber
Whither Organic Synthesis? [Review]

Daniel Janssen-Müller, Michael Schedler, Mirco Fleige, Constantin G. Daniliuc, Frank Glorius
Enantioselective Intramolecular Hydroacylation of Unactivated Alkenes: An NHC-Catalyzed Robust and Versatile Formation of Cyclic Chiral Ketones [Communication]

Enantioselective Intramolecular Hydroacylation of Unactivated Alkenes: An NHC-Catalyzed Robust and Versatile Formation of Cyclic Chiral Ketones

100 % Organic: A highly enantioselective N-heterocyclic carbene (NHC)-catalyzed intramolecular hydroacylation of aromatic and, more interestingly, aliphatic aldehydes with unactivated olefins offers access to a range of cyclic α-chiral ketones bearing quaternary centers. The reaction was found to be highly robust and proceeds with excellent yield in the presence of a diverse range of functional groups.

Angew. Chem. Int. Ed., March 16, 2015, DOI: 10.1002/anie.201412302

A Visible Light Photocatalytic Cross-Dehydrogenative Coupling/Dehydrogenation/6π-Cyclization/Oxidation Cascade: Synthesis of 12-Nitroindoloisoquinolines from 2-Aryltetrahydroisoquinolines

In one pot: A visible-light-induced photocatalytic cross-dehydrogenative coupling (CDC)/dehydrogenation/6π-cyclization/oxidation cascade converts common 2-aryl-1,2,3,4-tetrahydroisoquinolines into 12-nitro-substituted tetracyclic indolo[2,1-a]isoquinoline derivatives. Key to this new one-pot transformation is the presence of K3PO4 as a base and amino anthraquinone derivatives appear as superior organic photocatalysts.

Chem. Eur. J. 2015, 21, No. 23, 8336-8340

Eduardo Sánchez-Díez, Maitane Fernández, Uxue Uria, Efraim Reyes, Luisa Carrillo, Jose L. Vicario
Enantioselective Synthesis of Tertiary Propargylic Alcohols under N-Heterocyclic Carbene Catalysis [Communication]

Enantioselective Synthesis of Tertiary Propargylic Alcohols under N-Heterocyclic Carbene Catalysis

Ynones give the best: The enantioselective cross-benzoin reaction between aldehydes and ynones by employing a chiral N-heterocyclic carbene (NHC) as catalyst proceeds cleanly, not observing any by-product arising from competitive Stetter-type reactivity. This procedure allows the preparation of tertiary alkynyl carbinols as highly enantioenriched materials, which have the remarkable potential to be used as chiral building blocks in organic synthesis.

Chem. Eur. J. 2015, 21, No. 23, 8384-8388

Jian-Zhou Huang, Chen-Long Zhang, Yi-Fan Zhu, Lu-Lu Li, Dian-Feng Chen, Zhi-Yong Han, Liu-Zhu Gong
Organocatalytic Highly Enantioselective Substitution of 3-(1-Tosylalkyl)indoles with Oxindoles Enables the First Total Synthesis of (+)-Trigolutes B [Communication]

Organocatalytic Highly Enantioselective Substitution of 3-(1-Tosylalkyl)indoles with Oxindoles Enables the First Total Synthesis of (+)-Trigolutes B

A highly enantioselective organocatalytic substitution of 3-(1-tosylalkyl)indoles with oxindoles has been developed, providing an efficient approach to access highly enantioenriched 3,3'-disubstituted oxindoles, which are used as the key step in the total synthesis of (+)-trigolutes B.

Chem. Eur. J. 2015, 21, No. 23, 8389-8393

Chang Min, Chih-Tsung Lin, Daniel Seidel
Catalytic Enantioselective Intramolecular Aza-Diels–Alder Reactions [Communication]

Catalytic Enantioselective Intramolecular Aza-Diels–Alder Reactions

In control: A readily available chiral Brønsted acid was identified as an efficient catalyst for intramolecular Povarov reactions. Polycyclic amines containing three contiguous stereogenic centers were obtained with excellent stereocontrol in a single step from secondary anilines and aldehydes possessing a pendent dienophile. These transformations constitute the first examples of catalytic enantioselective intramolecular aza-Diels–Alder reactions.

Angew. Chem. Int. Ed. 2015, 54, No. 22, 6608-6612

Lei Wang, Qijian Ni, Marcus Blümel, Tao Shu, Gerhard Raabe, Dieter Enders
NHC-Catalyzed Asymmetric Synthesis of Functionalized Succinimides from Enals and α-Ketoamides [Communication]

NHC-Catalyzed Asymmetric Synthesis of Functionalized Succinimides from Enals and α-Ketoamides

Highly functionalized succinimides: The N-heterocyclic carbene (NHC)-catalyzed [3+2] cycloaddition of α-ketoamides with enals via an azolium enolate pathway stereoselectively leads to functionalized succinimides, which are characteristic structural features of various natural products and drugs (see scheme). By simply changing the NHC catalyst, the isomeric γ-lactones are obtained via an azolium homoenolate route.

Chem. Eur. J. 2015, 21, No. 22, 8033-8037

Dienamine and Friedel–Crafts One-Pot Synthesis, and Antitumor Evaluation of Diheteroarylalkanals

All in one: An asymmetric synthesis of diheteroarylalkanals through a one-pot dienamine and Friedel–Crafts reaction is presented (see scheme). The reaction tolerates a large variety of substituents at different positions of the starting aldehyde, and the use of nucleophiles and different diheterocyclic alkanals can also be achieved. The antiproliferative activity of these new compounds in different cancer tumor cell lines has also been investigated and it was found that, with the appropriate substitution, the compounds are as cytotoxic as Cisplatin.

Chem. Eur. J. 2015, 21, No. 22, 8237-8241

Marc Montesinos-Magraner, Carlos Vila, Rubén Cantón, Gonzalo Blay, Isabel Fernández, M. Carmen Muñoz, José R. Pedro
Organocatalytic Asymmetric Addition of Naphthols and Electron-Rich Phenols to Isatin-Derived Ketimines: Highly Enantioselective Construction of Tetrasubstituted Stereocenters [Communication]

Organocatalytic Asymmetric Addition of Naphthols and Electron-Rich Phenols to Isatin-Derived Ketimines: Highly Enantioselective Construction of Tetrasubstituted Stereocenters

Gentle persuasion: A quinine-derived thiourea organocatalyst was found to promote the asymmetric addition of naphthols and activated phenols to ketimines derived from isatins (see scheme; Boc=tert-butoxycarbonyl). The reaction under mild conditions afforded chiral 3-amino-2-oxindoles containing a quaternary stereocenter in high yields (up to 99 %) with excellent enantioselectivity (up to 99 % ee).

Angew. Chem. Int. Ed. 2015, 54, No. 21, 6320-6324

Peter G. K. Clark, Lucas C. C. Vieira, Cynthia Tallant, Oleg Fedorov, Dean C. Singleton, Catherine M. Rogers, Octovia P. Monteiro, James M. Bennett, Roberta Baronio, Susanne Müller, Danette L. Daniels, Jacqui Méndez, Stefan Knapp, Paul E. Brennan, Darren J. Dixon
LP99: Discovery and Synthesis of the First Selective BRD7/9 Bromodomain Inhibitor [Communication]

LP99: Discovery and Synthesis of the First Selective BRD7/9 Bromodomain Inhibitor

BRD7 and BRD9 are bromodomain proteins and part of some chromatin-remodeling complexes. A fragment lead was rapidly optimized through structure-based design and exploitation of a stereoselective nitro-Mannich/lactamization cascade process to give the first potent and selective BRD7/9 inhibitor, LP99. Treatment with LP99 led to displacement of BRD7 and BRD9 from chromatin and down-regulation of the pro-inflammatory cytokine IL-6.

Angew. Chem. Int. Ed. 2015, 54, No. 21, 6217-6221

Hironori Takeuchi, Kenji Mishiro, Yoshihiro Ueda, Yusuke Fujimori, Takumi Furuta, Takeo Kawabata
Total Synthesis of Ellagitannins through Regioselective Sequential Functionalization of Unprotected Glucose [Communication]

Total Synthesis of Ellagitannins through Regioselective Sequential Functionalization of Unprotected Glucose

Short and sweet: Very short total syntheses of ellagitannins were achieved through sequential and regioselective functionalization of the hydroxy groups of unprotected glucose.

Angew. Chem. Int. Ed. 2015, 54, No. 21, 6177-6180

Alejandro Parra, Mariola Tortosa
para-Quinone Methide: a New Player in Asymmetric Catalysis [Highlight]

para-Quinone Methide: a New Player in Asymmetric Catalysis

A new sheriff in town: para-Quinone methides (p-QMs) have been successfully used in asymmetric organocatalysis. Particularly, the asymmetric 1,6-addition of phenyl malonate and different aldehydes to 2,6-disubstituted p-QMs has provided a rapid access to important chiral diarylmethines, highlighting the importance of these synthetic intermediates. These new structures will open up the development of important asymmetric transformations in the future.

ChemCatChem 2015, 7, No. 10, 1524-1526

Riccardo Porta, Francesca Coccia, Rita Annunziata, Alessandra Puglisi
Comparison of Different Polymer- and Silica-Supported 9-Amino-9-deoxy-epi-quinines as Recyclable Organocatalysts [Full Paper]

Comparison of Different Polymer- and Silica-Supported 9-Amino-9-deoxy-epi-quinines as Recyclable Organocatalysts

Organic power for asymmetric catalysis: Properly modified 9-amino-epi-quinine derivatives are anchored onto different supports and used as efficient organocatalysts in a variety of reactions, in some cases outperforming their nonsupported counterparts. The immobilization also extends the catalyst lifetime.

ChemCatChem 2015, 7, No. 09, 1490-1499

Copper(I)-Catalysed Domino Coupling and Cyclisation Reaction: A Mild, Expedient Route for the Synthesis of Indene and Dihydronaphthalene Derivatives

Bench-top CuI has been used as a catalyst to obtain a series of functionalised indene, dihydronaphthalene and cyclohexenone derivatives. Notably, the substrates were combined at a 1:1 ratio and no trace of fumarate or maleate side products were observed in spite of using diazo substrate and copper catalyst.

Eur. J. Org. Chem. 2015, No. 14, 3141-3146

Alexis Castillo, Lucia Silva, David Briones, José F. Quílez del Moral, Alejandro F. Barrero
Collective Synthesis of Natural Products Sharing the Dihydro-γ-Ionone Core [Full Paper]

Collective Synthesis of Natural Products Sharing the Dihydro-γ-Ionone Core

The expedient enantioselective synthesis of several natural products from a common precursor, (+)-3,4-dihydro-γ-ionone, is described. The production of this natural compound in multigram scale from the extract Bellardia trixago is the basis of this approach.

Eur. J. Org. Chem. 2015, No. 15, 3266-3273

Hong-Wu Zhao, Bo Li, Ting Tian, Wei Meng, Zhao Yang, Xiu-Qing Song, Xiao-Qin Chen, Hai-Liang Pang
Highly Enantioselective Synthesis of Chiral Pyranonaphthoquinone-Fused Spirooxindoles through Organocatalytic Three-Component Cascade Reactions [Full Paper]

Highly Enantioselective Synthesis of Chiral Pyranonaphthoquinone-Fused Spirooxindoles through Organocatalytic Three-Component Cascade Reactions

In the presence of cinchona-thiourea catalyst C1, the developed organocascade three-component reaction of isatins, malononitrile, and 2-hydroxynaphthalene-1,4-diones readily proceeded to furnish desired chiral pyranonaphthoquinone-fused spirooxindoles in excellent chemical yields and high enantioselectivities (up to 99 % yield and 97 % ee).

Eur. J. Org. Chem. 2015, No. 15, 3320-3326

Design and Synthesis of Chiral Binaphthol-Derived Bisphosphoric Acids and Their Application in the Catalytic Enantioselective Hydrogenation of Quinolines

A little of bis, a little of that: A number of new chiral bisphosphoric acids were developed starting from (R)-BINOL. Rigid cyclic phosphamide and phosphonate components were converted into bisphosphoric acids, in contrast to the traditional BINOL-based phosphoric acids with only phosphonate motifs.

Asian J. Org. Chem. 2015, 4, No. 05, 430-433

Debashis Ghosh, Naveen Gupta, Sayed H. R. Abdi, Sekhar Nandi, Noor-ul H. Khan, Rukhsana I. Kureshy, Hari C. Bajaj
Organocatalyzed Enantioselective Allylation of Isatins by Using a Chiral Amino Alcohol Derived Squaramide as Catalyst [Short Communication]

Organocatalyzed Enantioselective Allylation of Isatins by Using a Chiral Amino Alcohol Derived Squaramide as Catalyst

A new series of squaramide-based organocatalysts were developed and successfully applied for the asymmetric allylation reaction of isatins with allyltributltin. The present catalytic system was highly efficient for the allylation of N-protected isatins giving very good yields (75–95 %) and excellent enantioselectivities (62–98 %) of the allylation products.

Eur. J. Org. Chem. 2015, No. 13, 2801-2806

Maxime Gicquel, Yang Zhang, Paul Aillard, Pascal Retailleau, Arnaud Voituriez, Angela Marinetti
Phosphahelicenes in Asymmetric Organocatalysis: [3+2] Cyclizations of γ-Substituted Allenes and Electron-Poor Olefins [Communication]

Phosphahelicenes in Asymmetric Organocatalysis: [3+2] Cyclizations of γ-Substituted Allenes and Electron-Poor Olefins

Helical P: Specially designed phosphahelicenes demonstrate high efficiency and enantioselectivity in organocatalytic cyclizations. These new helically chiral phosphines complement and outperform previous nucleophilic catalysts used in this field. Ipc*=(1R,2R,3R,5S)-2,6,6-trimethyl-bicyclo[3.1.1]-heptan-3-yl.

Angew. Chem. Int. Ed. 2015, 54, No. 18, 5470-5473

Enantioselective [3+2] Cyclization of 3-Isothiocyanato Oxindoles with Trifluoromethylated 2-Butenedioic Acid Diesters

Spiraling out of control: A highly efficient organocatalytic enantioselective [3+2] cyclization, which uses trifluoromethylated 2-butenedioic acid diesters for the formation of enantioenriched spiroxindoles that possess a CF3-containing quaternary carbon stereocenter, is explored. This procedure provides an enantiodivergent approach to the synthesis of spirooxindoles at different temperatures. Ts=p-Toluenesulfonyl, Bn=benzyl.

ChemCatChem 2015, 7, No. 08, 1366-1371

Jianfeng Xu, Xingkuan Chen, Ming Wang, Pengcheng Zheng, Bao-An Song, Yonggui Robin Chi
Aminomethylation of Enals through Carbene and Acid Cooperative Catalysis: Concise Access to β2-Amino Acids [Communication]

Aminomethylation of Enals through Carbene and Acid Cooperative Catalysis: Concise Access to β2-Amino Acids

Harmonious cooperation: An N-heterocyclic carbene (NHC) and (in situ generated) Brønsted acid cooperatively catalyze the aminomethylation of α,β-unsaturated aldehydes. This cooperative catalytic reaction provides a redox neutral strategy for quick access to β2-amino esters in an enantioselective manner.

Angew. Chem. Int. Ed. 2015, 54, No. 17, 5161-5165

Enamine Activation of β-Ketocarbonyls: New Opportunities in Enantioselective Organocatalysis

A revelation: Enamine activation of α-branched β-ketocarbonyl compounds is actually possible, very efficient, and highly enantioselective with a bifunctional primary amine/tertiary ammonium triflate salt catalyst. This covalent HOMO activation mode competes with existing strategies for the enantioselective activation of β-ketocarbonyls and their analogues. E=Electrophile; X=CH2, O, NR; OTf=Triflate.

ChemCatChem 2015, 7, No. 08, 1263-1264

Qiying Zhang, Xiuling Cui, Long Zhang, Sanzhong Luo, Hui Wang, Yangjie Wu
Redox Tuning of a Direct Asymmetric Aldol Reaction [Communication]

Redox Tuning of a Direct Asymmetric Aldol Reaction

Stay tuned: A redox tuning strategy has been developed for asymmetric aminocatalysis using a chiral ferrocenophane. Under redox control, the catalyst catalyzes the asymmetric aldol reaction at room temperature with excellent yield and good stereoselectivity. Moreover, the catalyst is recyclable.

Angew. Chem. Int. Ed. 2015, 54, No. 17, 5210-5213

Lorenzo Caruana, Martina Mondatori, Vasco Corti, Sara Morales, Andrea Mazzanti, Mariafrancesca Fochi, Luca Bernardi
Catalytic Asymmetric Addition of Meldrum’s Acid, Malononitrile, and 1,3-Dicarbonyls to ortho-Quinone Methides Generated In Situ Under Basic Conditions [Communication]

Catalytic Asymmetric Addition of Meldrum’s Acid, Malononitrile, and 1,3-Dicarbonyls to ortho-Quinone Methides Generated In Situ Under Basic Conditions

Challenging substrates: The generation in situ of ortho-quinone methides (o-QMs) through sulfinic acid elimination was combined for the first time with an organocatalytic process (see scheme). This combination allowed the engagement of sensitive and unstable o-QMs in asymmetric reactions with active methylene compounds, under the promotion of bifunctional catalysts, giving access to 2,3-dihydrocoumarins, 4H-chromenes, and xanthen-1-ones.

Chem. Eur. J. 2015, 21, No. 16, 6037-6041

Anitha Alanthadka, C. Uma Maheswari
N-Heterocyclic Carbene-Catalyzed Oxidative Amidation of Aldehydes with Amines [Communication]

Juhua Feng, Lili Lin, Kunru Yu, Xiaohua Liu, Xiaoming Feng
Asymmetric Synthesis of Dihydrofurans via Organocatalytic Domino Michael–Alkylation Reaction [Update]

Adam D. Gammack Yamagata, Swarup Datta, Kelvin E. Jackson, Linus Stegbauer, Robert S. Paton, Darren J. Dixon
Enantioselective Desymmetrization of Prochiral Cyclohexanones by Organocatalytic Intramolecular Michael Additions to α,β-Unsaturated Esters [Communication]

Enantioselective Desymmetrization of Prochiral Cyclohexanones by Organocatalytic Intramolecular Michael Additions to α,β-Unsaturated Esters

Enantioenriched derivatives of 2-azabicyclo[3.3.1]nonane, a key motif common to many alkaloids, are obtained by a catalytic asymmetric desymmetrization reaction with a cyclohexanediamine-derived primary-amine organocatalyst. A range of prochiral cyclohexanone derivatives with an α,β-unsaturated ester moiety linked to the 4-position afford the bicyclic products as single diastereoisomers in high enantioselectivity and good yields.

Angew. Chem. Int. Ed. 2015, 54, No. 16, 4899-4903

Rajesh Munirathinam, Jurriaan Huskens, Willem Verboom
Supported Catalysis in Continuous-Flow Microreactors [Review]

Catalytic Asymmetric Arylation of 3-Indolylmethanols: Enantioselective Synthesis of 3,3'-Bis(indolyl)oxindoles with High Atom Economy

Shifting economy: The catalytic enantioselective arylation of 3-indolylmethanols has been established in an atom-economic fashion, which assembles isatin-derived 3-indolylmethanols and 3-methylindoles into biologically important 3,3'-bis(indolyl)oxindoles bearing a quaternary stereogenic center in high yields and good enantioselectivities [≈99 % yield and 91:9 enantiomeric ratio (er)]. CPA=Chiral phosphoric acid.

ChemCatChem 2015, 7, No. 07, 1211-1221

Olivier Mahé, Jean-François Brière, Isabelle Dez
Chitosan: An Upgraded Polysaccharide Waste for Organocatalysis [Microreview]

Chitosan: An Upgraded Polysaccharide Waste for Organocatalysis

This microreview outlines recent advances in achiral to asymmetric organocatalytic reactions based on chitosan, a biodegradable chiral polysaccharide obtained from marine wastes, in a sustainable chemistry context. The use of chitosan and its derivatives either as insoluble organocatalysts or as supports for organocatalysts is reviewed, together with shaping and reusability issues.

Eur. J. Org. Chem. 2015, No. 12, 2559-2578

María de Gracia Retamosa, Abel de Cózar, Mirian Sánchez, José I. Miranda, José M. Sansano, Luis M. Castelló, Carmen Nájera, Ana I. Jiménez, Francisco J. Sayago, Carlos Cativiela, Fernando P. Cossío
Remote Substituent Effects on the Stereoselectivity and Organocatalytic Activity of Densely Substituted Unnatural Proline Esters in Aldol Reactions [Full Paper]

Remote Substituent Effects on the Stereoselectivity and Organocatalytic Activity of Densely Substituted Unnatural Proline Esters in Aldol Reactions

Densely substituted enantiopure proline esters obtained through [3+2] cycloadditions catalyze aldol reactions. These synthetic organocatalysts produce different enantiomeric aldol adducts depending on the stereochemical dispositions of the substituents at distal positions with respect to the catalytic site. Design criteria are proposed for this kind of organocatalysts.

Eur. J. Org. Chem. 2015, No. 11, 2503-2516

Huanrui Zhang, Baomin Wang, Longchen Cui, Xiaoze Bao, Jingping Qu, Yuming Song
Organocatalytic Asymmetric Fluorination of 4-Substituted Isoxazolinones [Short Communication]

Organocatalytic Asymmetric Fluorination of 4-Substituted Isoxazolinones

A straightforward method for the asymmetric fluorination of 4-substituted isoxazolinones catalyzed by a bis-cinchona alkaloid catalyst was developed. A series of 4-fluoroisoxazolinone derivatives with a fluorine-containing quaternary stereocenter were obtained in good to high yields with good enantioselectivities (up to 91 % yield, 85 % ee).

Eur. J. Org. Chem. 2015, No. 10, 2143-2147

Pyrimidine-Derived Prolinamides as Recoverable Bifunctional Organocatalysts for Enantioselective Inter- and Intramolecular Aldol Reactions under Solvent-Free Conditions

The intermolecular ketone–aldehyde and aldehyde–aldehyde aldol reactions and the Hajos–Parrish–Eder–Sauer–Wiechert versions with the employment of chiral L-prolinamides containing the (R,R)- and (S,S)-trans-cyclohexane-1,2-diamine scaffold and a 2-pyrimidinyl unit are successfully performed under solvent-free conditions; WMK = Wieland–Miescher ketone.

Eur. J. Org. Chem. 2015, No. 12, 2614-2621

Mareike C. Holland, Ryan Gilmour
Deconstructing Covalent Organocatalysis [Minireview]

Deconstructing Covalent Organocatalysis

In recent years, interest in organocatalytic intermediates has intensified. Through their study, various mechanistic anomalies have been illuminated, new reaction manifolds have been identified, and the intermediates themselves have proven to be valuable platforms for the study of many noncovalent interactions more commonly found in complex biomolecules. Cat=catalyst, P=product, S=substrate.

Angew. Chem. Int. Ed. 2015, 54, No. 13, 3862-3871

David Monge, Hao Jiang, Yolanda Alvarez-Casao
Masked Unsaturated Esters/Amides in Asymmetric Organocatalysis [Concept]

Masked Unsaturated Esters/Amides in Asymmetric Organocatalysis

Masked crusaders: This Concept article summarizes strategies regarding the use of masked unsaturated esters/amides in asymmetric organocatalysis (see scheme). Useful substrates are categorized by their inherent templates which enable interactions with organocatalysts and define their transformation back to the parent carboxylates. Examples showing the entire process (from substrates-to-functionalized esters/amides) are given.

Chem. Eur. J. 2015, 21, No. 12, 4494-4504

Constanze N. Neumann, Tobias Ritter
Late-Stage Fluorination: Fancy Novelty or Useful Tool? [Essay]

Late-Stage Fluorination: Fancy Novelty or Useful Tool?

Charming fluorine: This Essay examines the recent surge in late-stage fluorination reactions and outlines challenges that need to be overcome to increase the impact of modern fluorination methods on the synthesis of complex organofluorine compounds. It is outlined how an improved understanding of the bonding interactions of fluoride could lead to a new class of mild fluorinating reagents and a range of functional-group-tolerant reactions.

Angew. Chem. Int. Ed. 2015, 54, No. 11, 3216-3221

Lucia Anna Bivona, François Quertinmont, Hazi Ahmad Beejapur, Francesco Giacalone, Mireia Buaki-Sogo, Michelangelo Gruttadauria, Carmela Aprile
Thiazolium-Based Catalysts for the Etherification of Benzylic Alcohols under Solvent-Free Conditions [Full Paper]

Davide Ravelli, Maurizio Fagnoni
Aromatic Aldehydes as Energy-Transfer Photoorganocatalysts [Highlight]

Aromatic Aldehydes as Energy-Transfer Photoorganocatalysts

New photochemical life of ArCHO: The recent breakthrough discovery by Melchiorre and co-workers in the use of aromatic aldehydes as energy-transfer photoorganocatalysts in atom-transfer radical addition reactions is discussed. ISC=Intersystem crossing; X=I, Br, Cl.

ChemCatChem 2015, 7, No. 05, 735-737

Pankaj Chauhan, Suruchi Mahajan, Uğur Kaya, Daniel Hack, Dieter Enders
Bifunctional Amine-Squaramides: Powerful Hydrogen-Bonding Organocatalysts for Asymmetric Domino/Cascade Reactions [Review]

Organocatalysis on Tap: Enantioselective Continuous Flow Processes Mediated by Solid-Supported Chiral Organocatalysts

Modern continuous flow techniques are reshaping the chemical landscape by providing tools for more efficient chemical processes. Enantioselective catalysis can also benefit from these advantages, and the combination of these two fields is a perfect match in terms of sustainable chemistry. Here we focus on the use of immobilized organocatalysts to promote enantioselective processes in flow.

Eur. J. Org. Chem. 2015, No. 06, 1173-1188

Electrodes Functionalized with the 2,2,6,6-Tetramethylpiperidinyloxy Radical for the Waste-Free Oxidation of Alcohols

Selective oxidation with electricity only: Electrodes functionalized with the organocatalyst 2,2,6,6-tetramethylpiperidinyloxy (TEMPO) hold great potential for the development of the entirely waste-free industrial synthesis of valuable carbonyl compounds in the fine chemical and pharmaceutical industries.

ChemCatChem 2015, 7, No. 04, 552-558

Artificial Flavin Systems for Chemoselective and Stereoselective Oxidations

This review covers the design and applications of artificial flavinium-based organocatalytic systems for chemoselective and stereoselective oxygenations with hydrogen peroxide and oxygen as stoichiometric oxidising agents.

Eur. J. Org. Chem. 2015, No. 05, 915-932

Marek Dzięgielewski, Jakub Pięta, Elżbieta Kamińska, Łukasz Albrecht
Organocatalytic Synthesis of Optically Active Organophosphorus Compounds [Microreview]

Organocatalytic Synthesis of Optically Active Organophosphorus Compounds

Organophosphorus reagents play pivotal roles in modern organic synthesis and have found many applications for the preparation both of synthetically important compounds and of biologically relevant ones. They are now widely employed in asymmetric organocatalysis to afford optically active organophosphorus compounds. This review summarizes recent progress in this field of enantioselective synthesis.

Eur. J. Org. Chem. 2015, No. 04, 677-702

Mohammed Kadraoui, Thibault Maunoury, Zoubir Derriche, Stéphane Guillarme, Christine Saluzzo
Isohexides as Versatile Scaffolds for Asymmetric Catalysis [Microreview]

Isohexides as Versatile Scaffolds for Asymmetric Catalysis

Two series of dianhydrohexitol derivatives, the first preserving the original bis-fused THF backbones and the second originating from single THF ring-opening reactions, are used as asymmetric ligands in organometallic catalysis or as asymmetric organocatalysts. Their synthesis and their application in different asymmetric reactions for the formation of C–H, C–C, C–N, and C–S bonds are discussed.

Eur. J. Org. Chem. 2015, No. 03, 441-457

Rongwei Jin, Frederic W. Patureau
Metal-free Dehydrogenative Isoquinolone Synthesis [Highlight]

Metal-free Dehydrogenative Isoquinolone Synthesis

Versatile C-H bonds: We discuss Manna and Antonchick's metal-free isoquinolone synthesis through the dehydrogenative condensation of benzamides with alkynes and what it means for the fields of C-H functionalization and organic synthesis. DG=Directing group, E=electrophile.

ChemCatChem 2015, 7, No. 02, 223-225

A New Role for Sulfenate Anions: Organocatalysis

Introducing...Sulfenate! The sulfenate anion is introduced for the first time as a catalyst and was found to facilitate the conversion of benzyl halides to trans-stilbenes. CPME=Cyclopentyl methyl ether.

ChemCatChem 2015, 7, No. 02, 226-227

Enamine/Enolate-Mediated Organocatalytic Azide–Carbonyl [3+2] Cycloaddition Reactions for the Synthesis of Densely Functionalized 1,2,3-Triazoles

Organocatalytic click! Recent advances in the metal-free enamine/enolate-mediated azide–carbonyl [3+2] cycloaddition reaction are discussed. These approaches require neither a metal catalyst nor alkyne substrates. Owing to the ready availability of carbonyl compounds, these methods thus offer excellent alternatives for the synthesis of 1,4-/1,5-disubstituted and 1,4,5-trisubstituted 1,2,3-triazoles.

Angew. Chem. Int. Ed. 2014, 53, No. 52, 14310-14312

Promising Combination for Asymmetric Organocatalysis: Brønsted Acid-Assisted Chiral Phosphoric Acid Catalysis

Hand-in-hand: Recent developments in Brønsted acid-assisted chiral phosphoric acid catalysis are discussed, which exhibit the superiority of the self-assembly and the specificity of substrate recognition.

ChemCatChem 2014, 6, No. 12, 3309-3311

María D. Díaz-de-Villegas, José A. Gálvez, Ramón Badorrey, Pilar López-Ram-de-Víu
Organocatalysis in Enantioselective α-Functionalization of 2-Cyanoacetates [Review]

Applications of Carbohydrate-Based Organocatalysts in Enantioselective Synthesis

Carbohydrates, with their rigid backbones, large numbers of functional groups and high contents of chiral centres, are an appealing natural resource for the development of organocatalysts. They are becoming increasingly popular new tools for enantioselective synthesis, and this subject is reviewed for the period from 2009 to mid-2014.

Eur. J. Org. Chem. 2014, No. 33, 7291-7303

Charles C. J. Loh, Pankaj Chauhan, Daniel Hack, Christian Lehmann, Dieter Enders
Rapid Asymmetric Synthesis of Highly Functionalized Indanols via a Michael/Henry Organocascade with Submol% Squaramide Catalyst Loadings [Update]

Ophélie Quinonero, Cyril Bressy, Xavier Bugaut
Organocatalytic Enantioselective Construction of Polyaromatic Architectures [Highlight]

Organocatalytic Enantioselective Construction of Polyaromatic Architectures

Aromatics in 3D: Organocatalysis is now reaching beyond the control of stereogenic centers and opens new possibilities for the construction of complex polyaromatic structures with either helical or axial chirality.

Angew. Chem. Int. Ed. 2014, 53, No. 41, 10861-10863

Applications of Chiral Phosphine-Based Organocatalysts in Catalytic Asymmetric Reactions

Out with the old: The design and synthesis of new chiral phosphines, as well as their application in catalytic asymmetric reactions, have recently drawn a lot of attention. This review summarizes the advances in the field of enantioselective phosphine organocatalysis within the last couple of years.

Chem. Asian J. 2014, 9, No. 10, 2720-2734

Sylvain Oudeyer, Jean-François Brière, Vincent Levacher
Progress in Catalytic Asymmetric Protonation [Microreview]

Progress in Catalytic Asymmetric Protonation

This review provides an overview of recent advances in catalytic enantioselective protonation of preformed enol derivatives and catalytically generated enolates or equivalents through various cascade reaction sequences giving access to a large range of enantioenriched compounds containing tertiary stereocentres.

Eur. J. Org. Chem. 2014, No. 28, 6103-6119

Rebecca L. Davis, Julian Stiller, Tricia Naicker, Hao Jiang, Karl Anker Jørgensen
Asymmetric Organocatalytic Epoxidations: Reactions, Scope, Mechanisms, and Applications [Minireview]

Asymmetric Organocatalytic Epoxidations: Reactions, Scope, Mechanisms, and Applications

Pick your type: In the past several decades, highly useful epoxidation protocols have been developed with a variety of activation modes using a wide range of asymmetric organocatalysts. This review documents the rapid and expansive development in this area, thus providing a clear overview of the various catalyst types available for asymmetric organocatalytic epoxidations, as well as their mechanisms and applications.

Angew. Chem. Int. Ed. 2014, 53, No. 29, 7406-7426

Gloria Rassu, Vincenzo Zambrano, Luigi Pinna, Claudio Curti, Lucia Battistini, Andrea Sartori, Giorgio Pelosi, Giovanni Casiraghi, Franca Zanardi
Direct and Enantioselective Vinylogous Michael Addition of α-Alkylidenepyrazolinones to Nitroolefins Catalyzed by Dual Cinchona Alkaloid Thioureas [Update]

Catalytic Asymmetric α-Hydroxyamination of Carbonyls with N-Hydroxycarbamates Becomes Greener

The power of two: A highly enantio- and regioselective aminocatalytic and Lewis acid catalyzed α-hydroxyamination of β-keto esters and 1,3-diketones with N-hydroxycarbamates is realized in “one-pot” under aerobic conditions. The powerful dual catalysis strategy opens opportunities for developing new efficient organic transformations. Cbz=Benzyloxycarbonyl, Boc=tert-butoxycarbonyl.

ChemCatChem 2014, 6, No. 07, 1863-1865

Tyler J. Auvil, Andrew G. Schafer, Anita E. Mattson
Design Strategies for Enhanced Hydrogen-Bond Donor Catalysts [Microreview]

Design Strategies for Enhanced Hydrogen-Bond Donor Catalysts

Since initial reports of organocatalysis through hydrogen bonding interactions, a number of strategies have emerged to allow access to enhanced hydrogen-bond donor (HBD) organocatalysts. These strategies range from augmentation of existing HBDs to the design and synthesis of new HBD catalysts. The effects of recent dual HBD designs on catalyst performance are described.

Eur. J. Org. Chem. 2014, No. 13, 2633-2646

Organocatalytic β-Functionalization of Saturated Carbonyl Compounds—the State of the Art

Get straight to the point! The elusive and direct organocatalytic β-functionalization of saturated carbonyl compounds has been tackled by oxidative enamine catalysis, oxidative NHC catalysis and merging of photoredox catalysis with organocatalysis. This new activation mode expanded the horizons of chemical synthesis and offers new insight for organic transformations and complex molecule synthesis.

ChemCatChem 2014, 6, No. 05, 1183-1185

Yao Li, Xin Li, Jin-Pei Cheng
Catalytic Asymmetric Synthesis of Chiral Benzofuranones [Review]

The Alternative Route to Enantiopure Multicomponent Reaction Products: Biocatalytic or Organocatalytic Enantioselective Production of Inputs for Multicomponent Reactions

This review describes an approach to enantiopure products based on the enantioselective generation, through biocatalysis or organocatalysis, of chiral substrates for a multicomponent reaction (MCR). If the chiral substrates are able to control the newly formed stereogenic centers, this strategy allows fast and diversity-oriented entry to complex chiral substrates.

Eur. J. Org. Chem. 2014, No. 10, 2005-2015

Andrea Gualandi, Luca Mengozzi, Claire M. Wilson, Pier Giorgio Cozzi
Synergy, Compatibility, and Innovation: Merging Lewis Acids with Stereoselective Enamine Catalysis [Focus Review]

Synergy, Compatibility, and Innovation: Merging Lewis Acids with Stereoselective Enamine Catalysis

The Perfect Storm! Water facilitates catalyst turnover in enamine organocatalysis, and it is generated during enamine formation. A synergy between Lewis acids and organocatalysts allows for the development of new, selective, and innovative processes, but water-compatible Lewis acids must be employed that are capable of surviving and maintaining activity in the presence of water.

Chem. Asian J. 2014, 9, No. 04, 984-995

Chiral 1,1'-Binaphthyl-2,2'-Disulfonic Acid (BINSA) and Its Derivatives for Asymmetric Catalysis

BINSA, done that: The Brønsted acidity of catalysts is considered to be associated with their catalytic activity. Therefore, chiral 1,1'-binaphthyl-2,2-disulfonic acid (BINSA) has recently received much attention as a strong chiral Brønsted acid catalyst. This Focus Review summarizes the latest achievements in chiral BINSA chemistry from the perspective of their synthesis and their catalytic use in asymmetric organocatalysis.

Asian J. Org. Chem. 2014, 3, No. 04, 352-365

Suqing Zheng, Casi M. Schienebeck, Wei Zhang, Hao-Yuan Wang, Weiping Tang
Cinchona Alkaloids as Organocatalysts in Enantioselective Halofunctionalization of Alkenes and Alkynes [Focus Review]

Cinchona Alkaloids as Organocatalysts in Enantioselective Halofunctionalization of Alkenes and Alkynes

You say goodbye, I say halo: Derivatives of cinchona alkaloids are an important class of organocatalysts. Their applications in asymmetric halofunctionalization of alkenes and alkynes are summarized in this Focus Review. A wide range of nucleophiles, halogenation reagents, and substituted alkenes, alkynes, or enynes can participate in these reactions to afford diverse chiral building blocks.

Asian J. Org. Chem. 2014, 3, No. 04, 366-376

Frédéric-Georges Fontaine, Marc-André Courtemanche, Marc-André Légaré
Transition-Metal-Free Catalytic Reduction of Carbon Dioxide [Concept]

Transition-Metal-Free Catalytic Reduction of Carbon Dioxide

Less is more: Metal-free systems, including frustrated Lewis pairs (FLPs), have been shown to bind CO2. By reducing the Lewis acidity and basicity of the ambiphilic system, it is possible to generate active catalysts for the deoxygenative hydroboration of carbon dioxide to methanol derivatives with conversion rates comparable to those of transition-metal-based catalysts (see scheme).

Chem. Eur. J. 2014, 20, No. 11, 2990-2996

Haiying Du, Jean Rodriguez, Xavier Bugaut, Thierry Constantieux
Organocatalytic Enantioselective Multicomponent Synthesis of Pyrrolopiperazines [Update]

N-Heterocyclic Carbene Catalyzed Activation of Esters: A New Option for Asymmetric Domino Reactions

Esters—what else! A new strategy in NHC organocatalysis allows the α-, β- and γ-activation of saturated and unsaturated esters. The resulting acyl azolium intermediates efficiently participate in domino reactions with suitable substrates to generate synthetically valuable carbo- and heterocycles with very good diastereo- and excellent enantioselectivities.

Angew. Chem. Int. Ed. 2014, 53, No. 06, 1485-1487

© Wiley-VCH 2013.