N-Allylation of Azoles with Hydrogen Evolution Enabled by Visible-Light Photocatalysis.

Direct N-allylation of azoles with hydrogen evolution has been achieved through the synergistic combination of organic photocatalysis and cobalt catalysis. The protocol bypasses stoichiometric oxidants and prefunctionalization of alkenes and produces hydrogen (H2) as the byproduct. This transformation highlights high step- and atom-economy, high efficiency, and broad functional group tolerance for further derivatization, which opens a door for C-N bond formation that is valuable in heterocyclic chemistry.

[1]  Mark S. Taylor,et al.  Synergistic Organoboron/Palladium Catalysis for Regioselective N-Allylations of Azoles with Allylic Alcohols. , 2022, Organic letters.

[2]  C. Tung,et al.  Cobaloxime Photocatalysis for Phosphorylated Heteroaromatics. , 2022, Angewandte Chemie.

[3]  A. Lei,et al.  Site-selective amination towards tertiary aliphatic allylamines , 2022, Nature Catalysis.

[4]  Kalu Ram Bajya,et al.  Dual Photoredox and Cobalt Catalysis Enabled Transformations , 2022, European Journal of Organic Chemistry.

[5]  M. White,et al.  Allylic C–H amination cross-coupling furnishes tertiary amines by electrophilic metal catalysis , 2022, Science.

[6]  C. Tung,et al.  General and Efficient C-P Bond Formation by Quantum Dots and Visible Light , 2021, CCS Chemistry.

[7]  D. MacMillan,et al.  Metallaphotoredox: The Merger of Photoredox and Transition Metal Catalysis. , 2021, Chemical reviews.

[8]  Chao‐Jun Li,et al.  A cross-dehydrogenative C(sp3)−H heteroarylation via photo-induced catalytic chlorine radical generation , 2021, Nature Communications.

[9]  C. Yeung,et al.  Enantioselective Addition of Pyrazoles to Dienes. , 2021, Angewandte Chemie.

[10]  C. Tung,et al.  Direct Allylic C(sp3)-H and Vinylic C(sp2)-H Thiolation with Hydrogen Evolution by Quantum Dots and Visible Light. , 2021, Angewandte Chemie.

[11]  C. Tung,et al.  Quantum dots enable direct alkylation and arylation of allylic C(sp3)–H bonds with hydrogen evolution by solar energy , 2021, Chem.

[12]  Ding‐Wei Ji,et al.  Orthogonal Regulation of Nucleophilic and Electrophilic Sites in Pd-Catalyzed Regiodivergent Couplings between Indazoles and Isoprene. , 2021, Angewandte Chemie.

[13]  Bing Yu,et al.  4CzIPN-tBu-Catalyzed Proton-Coupled Electron Transfer for Photosynthesis of Phosphorylated N-Heteroaromatics. , 2020, Journal of the American Chemical Society.

[14]  M. Taillefer,et al.  Metal-Catalyzed Intermolecular Hydrofunctionalization of Allenes: Easy Access to Allylic Structures via the Selective Formation of C-N, C-C, and C-O Bonds. , 2020, Chemical reviews.

[15]  Joshua B. McManus,et al.  Homobenzylic Oxygenation Enabled by Dual Organic Photoredox and Cobalt Catalysis. , 2020, Journal of the American Chemical Society.

[16]  S. Matsunaga,et al.  The Merger of Photoredox and Cobalt Catalysis , 2020, Trends in Chemistry.

[17]  Zhenyang Lin,et al.  Site-specific allylic C–H bond functionalization with a copper-bound N-centred radical , 2019, Nature.

[18]  M. Muñoz,et al.  Platinum and Gold Catalysis: à la Carte Hydroamination of Terminal Activated Allenes with Azoles. , 2019, Organic letters.

[19]  A. Lei,et al.  Recent Advances in Oxidative R1-H/R2-H Cross-Coupling with Hydrogen Evolution via Photo-/Electrochemistry. , 2019, Chemical reviews.

[20]  S. W. Kim,et al.  Regio- and Enantioselective Iridium-Catalyzed N-Allylation of Indoles and Related Azoles with Racemic Branched Alkyl-Substituted Allylic Acetates. , 2019, Angewandte Chemie.

[21]  Chang Guo,et al.  Enantioselective γ-Addition of Pyrazole and Imidazole Heterocycles to Allenoates Catalyzed by Chiral Phosphine. , 2019, Angewandte Chemie.

[22]  Jian-Ping Qu,et al.  Iridium-Catalyzed Asymmetric Allylic Substitution Reactions. , 2019, Chemical reviews.

[23]  B. Breit,et al.  Palladium- and Rhodium-Catalyzed Dynamic Kinetic Resolution of Racemic Internal Allenes Towards Chiral Pyrazoles. , 2018, Angewandte Chemie.

[24]  Jie Wu,et al.  Photo-induced Decarboxylative Heck-Type Coupling of Unactivated Aliphatic Acids and Terminal Alkenes in the Absence of Sacrificial Hydrogen Acceptors. , 2018, Journal of the American Chemical Society.

[25]  Bin Chen,et al.  Photocatalytic Activation of Less Reactive Bonds and Their Functionalization via Hydrogen-Evolution Cross-Couplings. , 2018, Accounts of chemical research.

[26]  Jie Wu,et al.  Visible-Light-Mediated Metal-Free Hydrosilylation of Alkenes through Selective Hydrogen Atom Transfer for Si-H Activation. , 2017, Angewandte Chemie.

[27]  F. Rutjes,et al.  Pd-Catalyzed Hydroamination of Alkoxyallenes with Azole Heterocycles: Examples and Mechanistic Proposal , 2017, Organic letters.

[28]  Yang Li,et al.  Acceptorless Dehydrogenation of N-Heterocycles by Merging Visible-Light Photoredox Catalysis and Cobalt Catalysis. , 2017, Angewandte Chemie.

[29]  A. Singh,et al.  Photocatalytic Dehydrogenative Cross-Coupling of Alkenes with Alcohols or Azoles without External Oxidant. , 2017, Angewandte Chemie.

[30]  Ashutosh Kumar Singh,et al.  Anti-Markovnikov Oxidation of β-Alkyl Styrenes with H2O as the Terminal Oxidant. , 2016, Journal of the American Chemical Society.

[31]  Bin Chen,et al.  Photocatalytic Hydrogen-Evolution Cross-Couplings: Benzene C-H Amination and Hydroxylation. , 2016, Journal of the American Chemical Society.

[32]  Ke Chen,et al.  Scalable and Sustainable Electrochemical Allylic C–H Oxidation , 2016, Nature.

[33]  David A. Nicewicz,et al.  Experimental and Calculated Electrochemical Potentials of Common Organic Molecules for Applications to Single-Electron Redox Chemistry , 2015, Synlett.

[34]  Yi Pan,et al.  Metal-Free Catalytic Approach for Allylic C-H Amination Using N-Heterocycles via sp(3) C-H Bond Activation. , 2015, The Journal of organic chemistry.

[35]  David A. Nicewicz,et al.  Mechanistic Insight into the Photoredox Catalysis of Anti-Markovnikov Alkene Hydrofunctionalization Reactions , 2014, Journal of the American Chemical Society.

[36]  B. Liu,et al.  Cross-coupling hydrogen evolution reaction in homogeneous solution without noble metals. , 2014, Organic letters.

[37]  B. Breit,et al.  Atom-economic, regiodivergent, and stereoselective coupling of imidazole derivatives with terminal allenes. , 2014, Angewandte Chemie.

[38]  C. Tung,et al.  A cascade cross-coupling hydrogen evolution reaction by visible light catalysis. , 2013, Journal of the American Chemical Society.

[39]  A. Chan,et al.  An Efficient Oxidative Cross-Coupling Reaction between C–H and N–H Bonds; A Transition-Metal-Free Protocol at Room Temperature , 2013, Synlett.

[40]  David A. Nicewicz,et al.  Catalytic hydrotrifluoromethylation of styrenes and unactivated aliphatic alkenes via an organic photoredox system , 2013 .

[41]  M. Yus,et al.  Diastereoselective allylation of carbonyl compounds and imines: application to the synthesis of natural products. , 2013, Chemical reviews.

[42]  R. Schinazi,et al.  Cu(I)-catalyzed Huisgen azide-alkyne 1,3-dipolar cycloaddition reaction in nucleoside, nucleotide, and oligonucleotide chemistry. , 2009, Chemical reviews.

[43]  J. Hartwig,et al.  Regio- and enantioselective N-allylations of imidazole, benzimidazole, and purine heterocycles catalyzed by single-component metallacyclic iridium complexes. , 2009, Journal of the American Chemical Society.

[44]  T. Müller,et al.  Hydroamination: direct addition of amines to alkenes and alkynes. , 2008, Chemical reviews.

[45]  A. Schmidt,et al.  Recent Advances in the Chemistry of Indazoles , 2008 .

[46]  Peter G. Schultz,et al.  Noxious compounds activate TRPA1 ion channels through covalent modification of cysteines , 2007, Nature.

[47]  B. Trost,et al.  Asymmetric Transition Metal-Catalyzed Allylic Alkylations. , 1996, Chemical reviews.

[48]  Zhan Lu,et al.  Metal-catalyzed enantioselective allylation in asymmetric synthesis. , 2008, Angewandte Chemie.