Copper-Catalyzed Asymmetric Dearomative [3+2] Cycloaddition of Nitroheteroarenes with Azomethines

Catalytic asymmetric dearomative [3+2] cycloaddition of α-imino γ-lactones with either 3-nitroindoles or 2-nitrobenzofurans by using a chiral copper complex as the catalyst was developed. A wide range of structurally diverse polyheterocyclic compounds containing spirocyclic-fused butyrolactone-pyrrolidine-indoline and butyrolactone–pyrrolidine–dihydrobenzofuran skeletons could be smoothly obtained with excellent results (>99:1 dr and 98% ee). The potential synthetic applications of this methodology were also demonstrated by the scale-up experiment and by the diverse transformations of one product. This method is characterized by high asymmetric induction, wide functional group tolerance and scalability, and attractive product diversification.

[1]  A. Šačkus,et al.  Convenient Synthesis of N-Heterocycle-Fused Tetrahydro-1,4-diazepinones , 2022, Molecules.

[2]  Yuriy V. Gatilov,et al.  Oxidative [3+2]Cycloaddition of Alkynylphosphonates with Heterocyclic N-Imines: Synthesis of Pyrazolo[1,5-a]Pyridine-3-phosphonates , 2022, Molecules.

[3]  Kaikai Wang,et al.  Recent Progress of Electron‐Withdrawing‐Group‐Tethered Arenes Involved Asymmetric Nucleophilic Aromatic Functionalizations , 2022, Advanced Synthesis & Catalysis.

[4]  Jian‐Qiang Zhao,et al.  Organocatalyzed asymmetric dearomative 1,3-dipolar cycloaddition of 2-nitrobenzofurans and N-2,2,2-trifluoroethylisatin ketimines. , 2022, Chirality.

[5]  Kaizhi Li,et al.  Dearomatization of Nitro(hetero)arenes through Annulation , 2022, European Journal of Organic Chemistry.

[6]  Xin-Meng Chen,et al.  Ag-Catalyzed Asymmetric Interrupted Barton-Zard Reaction Enabling the Enantioselective Dearomatization of 2- and 3-Nitroindoles. , 2022, Organic letters.

[7]  Yi Yang,et al.  Dinuclear Zinc Catalyzed Enantioselective Dearomatization [3+2] Annulation of 2-Nitrobenzofurans and 2-Nitrobenzothiophenes. , 2021, Chemistry.

[8]  Jian‐Qiang Zhao,et al.  Catalytic Asymmetric Dearomative 1,3-Dipolar Cycloaddition of 2-Nitrobenzothiophenes and Isatin-Derived Azomethine Ylides. , 2021, Organic letters.

[9]  Jian‐Qiang Zhao,et al.  Catalytic asymmetric dearomative [4 + 2] annulation of 2-nitrobenzofurans and 5H-thiazol-4-ones: stereoselective construction of dihydrobenzofuran-bridged polycyclic skeletons , 2021, Organic Chemistry Frontiers.

[10]  Ł. Albrecht,et al.  Asymmetric Dearomative (3+2)-Cycloaddition Involving Nitro-Substituted Benzoheteroarenes under H-Bonding Catalysis , 2021, Molecules.

[11]  M. Zhang,et al.  Decarboxylative, Diastereoselective and exo-Selective 1,3-Dipolar Cycloaddition for Diversity-Oriented Construction of Structural Spiro[Butyrolactone–Pyrrolidine–Chromanone] Hybrids , 2021, Synlett.

[12]  Tianli Wang,et al.  Asymmetric Cyclodearomatization of 2‐Nitroindoles and 2‐Nitrobenzofurans for Constructing CF3‐containing Spiro‐polycycles by Bifunctional Phosphonium Salt Catalysis , 2021 .

[13]  Beeraiah Baire,et al.  Recent Dearomatization Strategies of Benzofurans and Benzothiophenes , 2021 .

[14]  S. You,et al.  Advances in Catalytic Asymmetric Dearomatization , 2021, ACS central science.

[15]  J. Legros,et al.  Reactivity of 3-nitroindoles with electron-rich species. , 2020, Chemical communications.

[16]  F. Shi,et al.  Progresses in organocatalytic asymmetric dearomatization reactions of indole derivatives , 2020, Organic Chemistry Frontiers.

[17]  Jian‐Qiang Zhao,et al.  Catalytic Enantioselective Dearomatization/Rearomatization of 2-Nitroindoles to Access 3-Indolyl-3'-Aryl-/Alkyloxindoles: Application in the Formal Synthesis of Cyclotryptamine Alkaloids. , 2020, Organic letters.

[18]  Shanliang Dong,et al.  [3+2]‐Cycloaddition of Catalytically Generated Pyridinium Ylide: A General Access to Indolizine Derivatives , 2020 .

[19]  Xiao-jie Li,et al.  Highly stereoselective construction of polycyclic benzofused tropane scaffolds and their latent bioactivities: bifunctional phosphonium salt-enabled cyclodearomatization process , 2020, Science China Chemistry.

[20]  M. Bandini,et al.  Recent Advances in the Catalytic Functionalization of “Electrophilic” Indoles , 2020 .

[21]  Zhen Wang,et al.  Enantioselective Synthesis of Fused Polycyclic Tropanes via Dearomative [3 + 2] Cycloaddition Reactions of 2-Nitrobenzofurans. , 2019, Organic letters.

[22]  S. You,et al.  Chiral phosphoric acid-catalyzed asymmetric dearomatization reactions. , 2019, Chemical Society reviews.

[23]  S. You,et al.  Catalytic asymmetric dearomatization (CADA) reaction-enabled total synthesis of indole-based natural products. , 2019, Natural product reports.

[24]  H. Niu,et al.  Facile synthesis of chiral [2,3]-fused hydrobenzofuran via asymmetric Cu(i)-catalyzed dearomative 1,3-dipolar cycloaddition. , 2019, Chemical communications.

[25]  Guanghao Huang,et al.  Recent Developments in Transition Metal‐Catalyzed Dearomative Cyclizations of Indoles as Dipolarophiles for the Construction of Indolines , 2018, Advanced Synthesis & Catalysis.

[26]  Xianxing Jiang,et al.  Asymmetric Synthesis of Bispiro[γ-butyrolactone-pyrrolidin-4,4′-pyrazolone] Scaffolds Containing Two Quaternary Spirocenters via an Organocatalytic 1,3-Dipolar Cycloaddition , 2018, European Journal of Organic Chemistry.

[27]  Chuanqiang Li,et al.  Diastereoselective construction of spirocyclic pyrrolidines bearing two quaternary centers via CuII-P, N-Ligand catalyzed 1,3-dipolar cycloaddition , 2017 .

[28]  S. You,et al.  Catalytic Asymmetric Dearomatization by Transition-Metal Catalysis: A Method for Transformations of Aromatic Compounds , 2016 .

[29]  F. Cossío,et al.  Enantioselective Synthesis of Polysubstituted Spiro-nitroprolinates Mediated by a (R,R)-Me-DuPhos·AgF-Catalyzed 1,3-Dipolar Cycloaddition. , 2016, Organic letters.

[30]  Liming Zhang,et al.  Catalytic asymmetric dearomatization (CADA) reactions of phenol and aniline derivatives. , 2016, Chemical Society reviews.

[31]  L. Stanley,et al.  Enantioselective dearomative [3 + 2] cycloadditions of indoles with azomethine ylides derived from alanine imino esters , 2016 .

[32]  T. Arai,et al.  PyBidine/copper catalyst: asymmetric exo'-selective [3+2] cycloaddition using imino ester and electrophilic indole. , 2014, Angewandte Chemie.

[33]  S. You,et al.  Transition-metal-catalyzed asymmetric allylic dearomatization reactions. , 2014, Accounts of chemical research.

[34]  B. Trost,et al.  Palladium-catalyzed dearomative trimethylenemethane cycloaddition reactions. , 2014, Journal of the American Chemical Society.

[35]  L. Wang,et al.  Efficient Construction of Highly Functionalized Spiro[γ-butyrolactone-pyrrolidin-3,3′-oxindole] Tricyclic Skeletons via an Organocatalytic 1,3-Dipolar Cycloaddition. , 2013 .

[36]  L. Wang,et al.  Efficient construction of highly functionalized spiro[γ-butyrolactone-pyrrolidin-3,3'-oxindole] tricyclic skeletons via an organocatalytic 1,3-dipolar cycloaddition. , 2013, Chemical communications.

[37]  Y. P. Bharitkar,et al.  Regio- and stereoselective synthesis of a library of bioactive dispiro-oxindolo/acenaphthoquino andrographolides via 1,3-dipolar cycloaddition reaction under microwave irradiation. , 2013, ACS combinatorial science.

[38]  Wei Zhang,et al.  Catalytic asymmetric dearomatization reactions. , 2012, Angewandte Chemie.

[39]  Chun‐Jiang Wang,et al.  Catalytic asymmetric construction of spiro(γ-butyrolactam-γ-butyrolactone) moieties through sequential reactions of cyclic imino esters with Morita-Baylis-Hillman bromides. , 2012, Chemistry.

[40]  H. Tao,et al.  Stereoselective construction of spiro(butyrolactonepyrrolidines) by highly efficient copper(I)/TF-BiphamPhos-catalyzed asymmetric 1,3-dipolar cycloaddition. , 2012, Chemistry.

[41]  Hong-min Liu,et al.  Highly efficient formal synthesis of cephalotaxine, using the Stevens rearrangement--acid lactonization sequence as a key transformation. , 2009, The Journal of organic chemistry.

[42]  L. Overman,et al.  Total synthesis of (+)-sarain A. , 2007, Journal of the American Chemical Society.

[43]  A. A. Raj,et al.  Synthesis, antimicrobial and antifungal activity of a new class of spiro pyrrolidines. , 2003, Bioorganic & medicinal chemistry.

[44]  Kinzo Matsumoto,et al.  Pteropodine and isopteropodine positively modulate the function of rat muscarinic M(1) and 5-HT(2) receptors expressed in Xenopus oocyte. , 2002, European journal of pharmacology.

[45]  D. Kingston,et al.  Bioactive indole alkaloids from the bark of Uncaria guianensis. , 1999, Planta medica.

[46]  Jian‐Qiang Zhao,et al.  Higher-order [10+2] cycloaddition of 2-alkylidene-1-indanones enables the dearomatization of 3-nitroindoles: an access to polycyclic cyclopenta[b]indoline derivatives , 2022, Organic Chemistry Frontiers.

[47]  Kemiao Hong,et al.  Recent Advances in Nitrene/Alkyne Metathesis Cascade Reaction , 2022, Chinese Journal of Organic Chemistry.

[48]  Liming Zhang,et al.  Recent Progress on Gold-catalyzed Dearomatization Reactions , 2017 .