Relay Organophotoredox/N-Heterocyclic Carbene Catalysis-Enabled Asymmetric Synthesis of Dibenzoxazepine-Fused Pyrrolidinones.

An unprecedented highly stereoselective synthesis of pyrrolo[1,2-d][1,4]oxazepin-3(2H)-ones has been accomplished via photoredox/N-heterocyclic carbene (NHC) relay catalysis. A wide range of substituted dibenzoxazepines and aryl/hetereoaryl enals were well accommodated under the organic photoredox catalysis-promoted amine oxidation to generate the imines, followed by a NHC-catalyzed [3 + 2] annulation reaction to achieve excellent diastereo- and enantioselectivities of the dibenzoxazepine-fused pyrrolidinones.

[1]  A. Biju,et al.  N-Heterocyclic Carbene-Catalyzed Umpolung of Cyclopent-4-ene-1,3-diones for Activated Olefin-Isatin Cross-Coupling. , 2022, Organic letters.

[2]  Bei Zhang,et al.  Acyldifluoromethylation Enabled by NHC-Photoredox Cocatalysis. , 2022, Organic letters.

[3]  Xin Huang,et al.  Catalytic Asymmetric Reductive Azaarylation of Olefins via Enantioselective Radical Coupling. , 2022, Journal of the American Chemical Society.

[4]  D. Sharma,et al.  Stereoselective Oxidative Mannich Reaction of Ketones with Dihydrodibenzo-oxazepines via a Merger of Photoredox-/Electro-catalysis with Organocatalysis. , 2022, ChemSusChem.

[5]  Yanli Yin,et al.  Asymmetric Hydroaminoalkylation of Alkenylazaarenes via Cooperative Photoredox and Chiral Hydrogen-Bonding Catalysis. , 2022, Angewandte Chemie.

[6]  Wang Yao,et al.  Asymmetric Photocatalysis Enabled by Chiral Organocatalysts , 2021, ChemCatChem.

[7]  A. Studer,et al.  Benzylic C−H acylation by cooperative NHC and photoredox catalysis , 2021, Nature Communications.

[8]  S. Ye,et al.  γ-Difluoroalkylation: Synthesis of γ-Difluoroalkyl-α,β-Unsaturated Esters via Photoredox NHC-Catalyzed Radical Reaction. , 2020, Organic letters.

[9]  A. Studer,et al.  Cooperative NHC and Photoredox Catalysis for the Synthesis of β‐Trifluoromethylated Alkyl Aryl Ketones , 2020, Angewandte Chemie.

[10]  T. Lu,et al.  Bio- and Medicinally Compatible α-Amino-Acid Modification via Merging Photoredox and N-Heterocyclic Carbene Catalysis. , 2020, Organic letters.

[11]  H. Ohmiya.  N-Heterocyclic Carbene-Based Catalysis Enabling Cross-Coupling Reactions , 2020, ACS Catalysis.

[12]  K. Scheidt,et al.  Combined Photoredox and Carbene Catalysis for the Synthesis of Ketones from Carboxylic Acids. , 2020, Angewandte Chemie.

[13]  S. Ye,et al.  Visible-Light-Driven N-Heterocyclic Carbene-catalyzed γ- and ε-Alkylation with Alkyl Radicals. , 2019, Angewandte Chemie.

[14]  C. Vila,et al.  A Combination of Visible-Light Organophotoredox Catalysis and Asymmetric Organocatalysis for the Enantioselective Mannich Reaction of Dihydroquinoxalinones with Ketones. , 2019, Organic letters.

[15]  U. K. Marelli,et al.  N-Heterocyclic Carbene-Catalyzed Umpolung of Imines for the Enantioselective Synthesis of Dihydroquinoxalines , 2019, ACS Catalysis.

[16]  Zhiyong Jiang,et al.  Organocatalytic Enantioselective Addition of α-Aminoalkyl Radicals to Isoquinolines. , 2018, Organic letters.

[17]  X. Pannecoucke,et al.  Synthesis of 4-Difluoromethylquinolines by NHC-Catalyzed Umpolung of Imines. , 2018, Organic letters.

[18]  C. Vila,et al.  Catalytic Asymmetric Reactions Involving the Seven‐Membered Cyclic Imine Moieties Present in Dibenzo[b,f][1,4]oxazepines , 2018 .

[19]  Guoxian Zhang,et al.  N-Heterocyclic Carbene-Catalyzed Umpolung of β,γ-Unsaturated 1,2-Diketones. , 2018, Organic letters.

[20]  D. MacMillan,et al.  Direct, enantioselective α-alkylation of aldehydes using simple olefins. , 2017, Nature chemistry.

[21]  C. Tung,et al.  Visible-Light-Promoted Asymmetric Cross-Dehydrogenative Coupling of Tertiary Amines to Ketones by Synergistic Multiple Catalysis. , 2017, Angewandte Chemie.

[22]  D. MacMillan,et al.  Photoredox Catalysis in Organic Chemistry , 2016, The Journal of organic chemistry.

[23]  D. Uraguchi,et al.  Synergistic Catalysis of Ionic Brønsted Acid and Photosensitizer for a Redox Neutral Asymmetric α-Coupling of N-Arylaminomethanes with Aldimines. , 2015, Journal of the American Chemical Society.

[24]  T. Rovis,et al.  Organocatalytic Reactions Enabled by N-Heterocyclic Carbenes. , 2015, Chemical reviews.

[25]  F. Glorius,et al.  An overview of N-heterocyclic carbenes , 2014, Nature.

[26]  Frank Glorius,et al.  Dual catalysis sees the light: combining photoredox with organo-, acid, and transition-metal catalysis. , 2014, Chemistry.

[27]  D. MacMillan,et al.  Enantioselective direct α-amination of aldehydes via a photoredox mechanism: a strategy for asymmetric amine fragment coupling. , 2013, Journal of the American Chemical Society.

[28]  D. MacMillan,et al.  Visible light photoredox catalysis with transition metal complexes: applications in organic synthesis. , 2013, Chemical reviews.

[29]  T. Rovis,et al.  Catalytic asymmetric α-acylation of tertiary amines mediated by a dual catalysis mode: N-heterocyclic carbene and photoredox catalysis. , 2012, Journal of the American Chemical Society.

[30]  K. Zeitler,et al.  Metal-free, cooperative asymmetric organophotoredox catalysis with visible light. , 2011, Angewandte Chemie.

[31]  Mark E. Scott,et al.  Enantioselective alpha-trifluoromethylation of aldehydes via photoredox organocatalysis. , 2009, Journal of the American Chemical Society.

[32]  J. Bode,et al.  Cyclic ketimines as superior electrophiles for NHC-catalyzed homoenolate additions with broad scope and low catalyst loadings. , 2008, Journal of the American Chemical Society.

[33]  K. Carlin,et al.  Dibenzazepines and dibenzoxazepines as sodium channel blockers. , 2015, Bioorganic & medicinal chemistry letters.

[34]  P. Blain.  Tear Gases and Irritant Incapacitants , 2003, Toxicological reviews.