Azine Activation via Silylium Catalysis

Practical, efficient, and general methods for the diversification of N-heterocycles have been a recurrent goal in chemical synthesis due to the ubiquitous influence of these motifs within bioactive frameworks. Here, we describe a direct, catalytic, and selective functionalization of azines via silylium activation. Our catalyst design enables mild conditions and a remarkable functional group tolerance in a one-pot setup.

[1]  J. Ouyang,et al.  Strong and Confined Acids Catalyze Asymmetric Intramolecular Hydroarylations of Unactivated Olefins with Indoles , 2021, Journal of the American Chemical Society.

[2]  K. Gademann,et al.  Nucleophilic Attack on Nitrogen in Tetrazines by Silyl-Enol Ethers. , 2020, Organic letters.

[3]  B. List,et al.  Confinement as a Unifying Element in Selective Catalysis , 2020, Chem.

[4]  B. List,et al.  Chiral Brønsted Acids Catalyze Asymmetric Additions to Substrates that Are Already Protonated: Highly Enantioselective Disulfonimide-Catalyzed Hantzsch Ester Reductions of NH–Imine Hydrochloride Salts , 2020, Synlett.

[5]  M. Baik,et al.  ZnMe2-Mediated, Direct Alkylation of Electron Deficient N-Heteroarenes with 1,1-Diborylalkanes: Scope and Mechanism. , 2020, Journal of the American Chemical Society.

[6]  S. Buchwald,et al.  Evidence for Simultaneous Dearomatization of Two Aromatic Rings Under Mild Conditions in Cu(I)-Catalyzed Direct Asymmetric Dearomatization of Pyridine. , 2020, Journal of the American Chemical Society.

[7]  P. Fier,et al.  A Multifunctional Reagent Designed for the Site-Selective Amination of Pyridines. , 2020, Journal of the American Chemical Society.

[8]  H. Klare,et al.  Cationic silicon Lewis acids in catalysis , 2019, Nature Reviews Chemistry.

[9]  Yiting Gu,et al.  A Mild and Direct Site-Selective sp2 C-H Silylation of (Poly)Azines. , 2018, Journal of the American Chemical Society.

[10]  B. List,et al.  IDPi Catalysis. , 2019, Angewandte Chemie.

[11]  I. Krossing,et al.  Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions. , 2018, Angewandte Chemie.

[12]  Jinho Kim,et al.  Efficient dehydrogenation of 1,2,3,4-tetrahydroquinolines mediated by dialkyl azodicarboxylates , 2018 .

[13]  S. Buchwald,et al.  Asymmetric Cu-Catalyzed 1,4-Dearomatization of Pyridines and Pyridazines without Preactivation of the Heterocycle or Nucleophile. , 2018, Journal of the American Chemical Society.

[14]  P. Fier.  A Bifunctional Reagent Designed for the Mild, Nucleophilic Functionalization of Pyridines. , 2017, Journal of the American Chemical Society.

[15]  F. Worek,et al.  Regioselective and Transition-Metal-Free Addition of tert-Butyl Magnesium Reagents to Pyridine Derivatives: A Convenient Method for the Synthesis of 3-Substituted 4-tert-Butylpyridine Derivatives , 2017, Synthesis.

[16]  M. Klussmann,et al.  Asymmetric counteranion-directed Lewis acid organocatalysis for the scalable cyanosilylation of aldehydes , 2016, Nature Communications.

[17]  Hisashi Yamamoto,et al.  Second Generation of Aldol Reaction. , 2016, Accounts of chemical research.

[18]  Sukbok Chang,et al.  Selective Silylative Reduction of Pyridines Leading to Structurally Diverse Azacyclic Compounds with the Formation of sp³ C-Si Bonds. , 2015, Journal of the American Chemical Society.

[19]  T. Müller,et al.  Quantitative Assessment of the Lewis Acidity of Silylium Ions , 2015 .

[20]  Theresa Fischer,et al.  Highly Enantioselective Nucleophilic Dearomatization of Pyridines by Anion-Binding Catalysis. , 2015, Angewandte Chemie.

[21]  B. List,et al.  Development and Applications of Disulfonimides in Enantioselective Organocatalysis. , 2015, Chemical reviews.

[22]  Edward L. Conn,et al.  Expedient synthesis of α-(2-azaheteroaryl) acetates via the addition of silyl ketene acetals to azine-N-oxides. , 2014, Organic letters.

[23]  Sabine Hadida,et al.  Addition of α-Lithiated Nitriles to Azaheterocycles , 2014 .

[24]  S. Denmark,et al.  Silyl ketene imines: highly versatile nucleophiles for catalytic, asymmetric synthesis. , 2012, Angewandte Chemie.

[25]  K. Baldridge,et al.  Proton-Catalyzed, Silane-Fueled Friedel-Crafts Coupling of Fluoroarenes , 2011, Science.

[26]  V. M. Vlasov,et al.  A comprehensive self-consistent spectrophotometric acidity scale of neutral Brønsted acids in acetonitrile. , 2006, The Journal of organic chemistry.

[27]  E. Corey,et al.  Selective 4-arylation of pyridines by a nonmetalloorganic process. , 2005, Organic letters.

[28]  D. Schuster,et al.  The Anomalous Reactivity of Fluorobenzene in Electrophilic Aromatic Substitution and Related Phenomena , 2003 .

[29]  Mustanir,et al.  Binding Interaction of the Trimethylsilyl Cation with Oxygen and Nitrogen Bases in the Gas Phase. Acetopheones, Benzaldehydes, Pyridines, Anilines, and N,N-Dimethylanilines , 2000 .

[30]  C. Reed.  The Silylium Ion Problem, R3Si+. Bridging Organic and Inorganic Chemistry , 1998 .

[31]  D. D. Perrin,et al.  Purification of Laboratory Chemicals , 2022 .