Organocatalysis :: Wiley-VCH Hot Topics

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Organocatalysis
The term organocatalysis describes the acceleration of chemical reactions through theaddition 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 theconcept and, more importantly, the fact that the efficiency and selectivity of manyorganocatalytic 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.
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Asymmetric Mannich Reaction of Aryl Methyl Ketones with Cyclic Imines Benzo[e][1,2,3]oxathiazine 2,2-Dioxides
Catalyzed by Cinchona Alkaloid-based Primary Amines
An asymmetric Mannich reaction of various aryl methyl ketones (acetophenonederivatives) with different substituted cyclic imine benzo[e][1,2,3]oxathiazine
2,2-dioxides has been developed using an alkaloid-derived primary amine asorganocatalyst, providing benzo-fused cyclic sulfamidate N-heterocycles with 85-98% ee.
[Full Paper]
Xiao-Yu Cui, Hui-Xin Duan, Yongna Zhang, You-Qing Wang
Chem. Asian J., September 30, 2016, DOI: 10.1002/asia.201601149. Read article
Nitroxyl-Radical-Catalyzed Oxidative Coupling of Amides with Silylated Nucleophiles through N-Halogenation
A halo to make them shine: A
high-yielding nitroxyl-radical-catalyzed
oxidative coupling reaction between
amines protected with an electronwithdrawing group and silylated
nucleophiles proceeded through theactivation of N-halogenated amides by thenitroxyl-radical catalyst to give imines. The N-halogenated amide intermediates were generated in situ from amides bytreatment with a halogenation reagent (see scheme).
[Communication]
Katsuhiko Moriyama, Masako Kuramochi, Kozo Fujii, Tsuyoshi Morita, Hideo Togo
Angew. Chem. Int. Ed., September 29, 2016, DOI: 10.1002/anie.201607223. Read article
Heteroatom Tuning of Bimolecular Criegee Reactions and Its Implications
Gas-phase reactions: The calculated barriers for the bimolecular reactions of Criegee intermediates and H2X inverselycorrelate with the bond strength of X−H bond of H2X or directly correlate with the first pKa value of H2X. Thus, it is not only
the substitutions of Criegee intermediates but also the properties of the heteroatom in H2X that play a crucial role indetermining the reactivity.
[Communication]
Manoj Kumar, Joseph S. FranciscoAngew. Chem. Int. Ed., September 28, 2016, DOI: 10.1002/anie.201604848. Read article

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Sequential NHC-Catalyzed Reaction of Enals and Cyclic Aryldiene-1,3-Diones: Synthesis of Tricyclic Chromenones
and Related Compounds.
N-heterocyclic carbene (NHC) catalyzed synthesis of highly functionalized pyrano[3,2-c]chromene-2,5-dione derivatives,
pyrano[3,2-c]quinoline-2,5(6H)-dione derivatives and pyrano[4,3-b]pyran-2,5-dione derivatives with potential biologicalactivities is reported. The reaction occurs via a Knoevenagel condensation and NHC-catalyzed enolate addition in one pot.
[Communication]
Vijay Nair, JAGADEESH KRISHNAN, SNEHA MATHEW, ANJANA JAYAPRAKASH P, SASIDHAR B. S., MAYADEVI T. S.,SURESH E.
Asian J. Org. Chem., September 27, 2016, DOI: 10.1002/ajoc.201600419. Read article
Carbon Dioxide Based N-Formylation of Amines Catalyzed by Fluoride and Hydroxide Anions
I've got anion you: A simple approach for theN-formylation of aliphatic and aromaticamines with CO2 and hydrosilane reducingagents at room temperature and atmosphericpressure is described. Fluoride and hydroxidesalts efficiently catalyze the reaction,
principally through activation of thehydrosilanes. Using n-Bu4NF as a simple
ammonium salt catalyst, the N-formylated
products are obtained in excellent yields withhigh selectivities.
[Communication]
Martin Hulla, Felix D. Bobbink, Shoubhik Das, Paul J. Dyson
ChemCatChem, September 26, 2016, DOI: 10.1002/cctc.201601027. Read article
Iodoalkyne-Based Catalyst-Mediated Activation of Thioamides through Halogen Bonding
Building relationships: An iodoalkyne bearing a pentafluorophenyl group was foundto be effective in the catalytic activation of thioamides through halogen bonding. The
thus activated thioamides reacted with 2-aminophenol to produce benzoxazoles ingood yield. Mechanistic studies provided concrete evidence that this catalytic
activation is based on halogen bonding.
[Communication]
Akinobu Matsuzawa, Shiho Takeuchi, Kazuyuki Sugita
Chem. Asian J., September 21, 2016, DOI: 10.1002/asia.201601130. Read article

Organocatalyzed Assembly of Chlorinated Quaternary Stereogenic Centers
The catalytic asymmetric construction of chiral quaternary stereocenters is always a continuous area of research in organic
chemistry. In this sense, when a chlorine atom takes part in a quaternary stereocenter, the difficulty of its synthesis
increases along with the significance of the resulting products. This is true, not only because of the intrinsic interest of suchchlorinated molecules, but also because they are considered as highly valuable chiral building blocks in organic synthesis,as they can be easily converted to more complexes molecules by a simple SN2 displacement. Among the different
strategies followed to create chlorinated quaternary stereogenic centers, organocatalysis has played a pivotal role during
the last decade. In this review, a comprehensive analysis of such organocatalyzed transformations is presented.
[Focus Review]
Melania Gómez-Martínez, Diego A. Alonso, Isidro M. Pastor, Gabriela Guillena, Alejandro Baeza
Asian J. Org. Chem., September 20, 2016, DOI: 10.1002/ajoc.201600404. Read article
Insights into N-Heterocyclic Carbene-Catalyzed [4 + 2] Annulation Reaction of Enals with Nitroalkenes:
Mechanisms, Origin of Chemo- and Stereoselectivity, and Role of Catalyst
In this paper, the density functional theory (DFT) has been employed to investigate the detailed mechanisms, origin ofchemo- and stereoselectivity, and role of catalyst for the reaction of enals with nitroalkenes catalyzed by N-heterocycliccarbene (NHC). The calculated results disclose that the reaction contains seven steps, i.e., the nucleophilic attack on the ,-unsaturated aldehyde by NHC, the [1, 2]-proton transfer for the formation of Breslow intermediate, the -protonation for

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affording enolate intermediate, the nucleophilic addition on the Re/Si face of enolate by the nitroalkenes, the [1, 5] protontransfer, the ring-closure process, and the regeneration of NHC. The addition on the Re/Si face of enolate is identified to be
the stereocontrolling step, in which the chiral centers including -carbon of enals and -carbon of nitroalkenes are formed.
Moreover, the reaction pathway leading to the RR-configured product has the lowest Gibbs free energy barrier, which is inagreement with the experimental observation. Furthermore, the analyses of electrophilic and nucleophilic Parr functions andglobal reactivity indexes (GRIs) have been performed to explore the origin of chemoselectivity and the role of catalyst. This
theoretical work would provide valuable insights for the rational design of more effective organocatalyst for this kind ofreactions with high stereoselectivities.
[Full Paper]
Linjie Zheng, Donghui Wei, Yang Wang, Yan Qiao
Chem. Asian J., September 08, 2016, DOI: 10.1002/asia.201601022. Read article
Kinetically Controlled α-Selective O-Glycosylation of Phenol Derivatives Using 2-Nitroglycals by a Bifunctional
Chiral Thiourea Catalyst
The highly α-selective organocatalytic
glycosylation of phenol derivatives using2-nitroglycals has been developed. The
stereoselectivity of this reaction was kineticallycontrolled by a bifunctional thiourea catalyst,
and was applied to synthesis of glycopeptides.
[Communication]
Keisuke Yoshida, Yohei Kanoko, Kenichi Takao
Asian J. Org. Chem., August 25, 2016, DOI: 10.1002/ajoc.201600307. Read article
Facile Preparation of Flavinium Organocatalysts
The green route: N(5)-Ethylated flavinium organocatalyst can be readily preparedwithout using any hazardous chemicals or inert atmosphere as previously required.
This work breaks the limited application of flavinium oxidation catalysts in bothlaboratory and industrial synthesis.
[Communication]
Yukihiro Arakawa, Takahiro Oonishi, Takahiro Kohda, Keiji Minagawa, Yasushi
Imada
ChemSusChem, August 24, 2016, DOI: 10.1002/cssc.201600846. Read article

Promotion of Organic Reactions by Non-Benzenoid Carbocylic Aromatic Ions
[Review]
Demelza J. M. Lyons, Reece D. Crocker, Marcus Blümel, Thanh Vinh NguyenAngew. Chem. Int. Ed., August 10, 2016, DOI: 10.1002/anie.201605979. Read article
Synthesis of Diheteroatomic Five-Membered Heterocyclic Compounds from α,β-Unsaturated Aldehydes
Channel 5: This Focus Review summarizes recent methods for the synthesis offive-membered N,N-, N,O-, and N,S-heterocycles based on the transformations of2-alkenals. A multitude of catalytic and technological novelties, such as asymmetricmetal- and organocatalysis, one-pot multicomponent reactions that proceed throughdomino, cascade, or tandem sequences, and microwave activation, have been used
to afford a diverse range of products.
[Focus Review]
N. A. Keiko, N. V. Vchislo
Asian J. Org. Chem., August 01, 2016, DOI: 10.1002/ajoc.201600227. Read article
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 avaluable tool for examining the mechanism of an enantioselective catalytic process. By comparing the results from theforward and back reaction, direct evidence for the involvement of a catalytic intermediate in the enantioselective step canbe 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

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[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.

N-Heterocyclic Carbene-Catalyzed Synthesis of Multi-Substituted Benzenes from Enals and α-Cyanoβ-methylenones[Communication]
Chun-Lin Zhang, Zhong-Hua Gao, Zhi-Qin Liang, Song YeAdv. Synth. Catal., June 20, 2016, DOI: 10.1002/adsc.201600531. Readarticle.

An Atropisomerically Enforced Phosphoric Acid for Organocatalytic Asymmetric Reactions
Three atropisomeric phosphoric acids for organocatalysis wereobtained by a single Suzuki coupling reaction, and resolved byHPLC. All three catalysts could be used to promoteorganocatalytic reactions, rendering up to excellent
enantioselectivity (98 % ee), confirming the potential ofatropisomeric conformational control at the 3,3'-position of theBINOL core to infuence catalyst performance.
[Full Paper]
Luca Bernardi, Giada Bolzoni, Mariafrancesca Fochi, Michele Mancinelli, Andrea MazzantiEur. 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
This review demonstrates the catalytic
efficiency of primary β-amino alcohols andtheir derivatives in organocatalysis. These
simple amino alcohols are inexpensivealternatives to other primary aminoorganocatalysts, 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
Drop the base: A novel catalytic system basedon a readily available phosphine oxide precatalyst
for base-free catalytic Wittig reactions has beendeveloped (see scheme). Under the optimized
reaction conditions, numerous functionalized
alkenes were prepared in yields up to 99 % andwith good to excellent E/Z selectivities.
[Full Paper]
Marie-Luis Schirmer, Sven Adomeit, Anke
Spannenberg, Thomas WernerChem. 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

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An innovative and flexible methodology catalyzed by bifunctional chiral thioureas
was developed to react β-nitro oxindoles with aldehydes (see scheme). Thisapproach allows the first enantioselective synthesis of 3-spiro-α-alkylideneγ-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
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 thebelieved 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
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(vinylalcohol), unnatural amino acids, and medicine (see graphic). This Minireview summarizes amethodologically diverse approach to the synthesis of target molecules by outlining a diverse array ofreactions 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
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 rangeof 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?
[Review]
Douglass F. Taber
Isr. J. Chem., April 15, 2015, DOI: 10.1002/ijch.201500006. Read article© Wiley-VCH 2015.

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