Palladium-catalyzed asymmetric formal [3+2] cycloaddition of α-N-heterocyclic acrylates with vinyl epoxides for construction of isonucleoside analogs.

A highly efficient Pd-catalyzed asymmetric formal [3+2] cycloaddition using α-N-heterocyclic acrylates to react with vinyl epoxides has been achieved for the first time to access chiral functionalized tetrahydrofuran skeletons (34 examples, up to 93% yield, >20 : 1 dr and 99% ee). Meanwhile, using a palladium/(S,S)-tBu-FOXAP catalyst or a palladium/(R)-Segphos catalyst, purine or pyrimidine isonucleoside analogs are constructed in high yields and stereoselectivity, respectively. The commercial availability of the catalysts, broad substrate scope and easy transformation of the products make this methodology an attractive method in asymmetric synthesis.

[1]  Wen Ding,et al.  Electron-Deficient Alkynes as Dipolarophile in Pd-Catalyzed Enantioselective (3 + 2) Cycloaddition Reaction with Vinyl Cyclopropanes. , 2019, Organic letters.

[2]  B. Trost,et al.  New Catalytic Asymmetric Formation of Oxygen Heterocycles Bearing Nucleoside Bases at the Anomeric Carbon. , 2019, Journal of the American Chemical Society.

[3]  Qiying Zhang,et al.  Asymmetric Transfer Hydrogenation of rac-α-(Purin-9-yl)cyclopentones via Dynamic Kinetic Resolution for the Construction of Carbocyclic Nucleosides. , 2019, Organic letters.

[4]  W. Xiao,et al.  A photoinduced Wolff rearrangement/Pd-catalyzed [3+2] cycloaddition sequence: an unexpected route to tetrahydrofurans. , 2019, Chemical communications.

[5]  Wenqin Wu,et al.  Trisubstituted alkenes with a single activator as dipolarophiles in a highly diastereo- and enantioselective [3+2] cycloaddition with vinyl epoxides under Pd-catalysis. , 2018, Chemical communications.

[6]  Jiong Cheng,et al.  Asymmetric Decarboxylative Cycloaddition of Vinylethylene Carbonates with β-Nitroolefins by Cooperative Catalysis of Palladium Complex and Squaramide , 2018, ACS Catalysis.

[7]  H. Niu,et al.  Synthesis of Chiral Six-Membered Carbocyclic Purine Nucleosides via Organocatalytic Enantioselective [3 + 3] Annulation. , 2018, Organic Letters.

[8]  B. Trost,et al.  Enantioselective Palladium-Catalyzed [3+2] Cycloaddition of Trimethylenemethane and Fluorinated Ketones. , 2018, Angewandte Chemie.

[9]  Chang-Hua Ding,et al.  Palladium/ N-Heterocyclic Carbene (NHC)-Catalyzed Asymmetric [3 + 2] Cycloaddition Reaction of Vinyl Epoxides with Allenic Amides. , 2018, Organic letters.

[10]  Yao-Wei Gao,et al.  Regio- and Enantioselective [3+2] Cycloaddition of α-Purine Substituted Acrylates with Allenes: An Approach to Chiral Carbocyclic Nucleosides , 2018, Advanced Synthesis & Catalysis.

[11]  Yong Jian Zhang,et al.  Pd-Catalyzed asymmetric decarboxylative cycloaddition of vinylethylene carbonates with 3-cyanochromones. , 2018, Chemical communications.

[12]  Yinlong Guo,et al.  Stereodivergent Synthesis of Tetrahydrofuroindoles through Pd-Catalyzed Asymmetric Dearomative Formal [3+2] Cycloaddition. , 2018, Angewandte Chemie.

[13]  Qiying Zhang,et al.  Enantioselective Synthesis of Carbocyclic Nucleosides via Asymmetric [3 + 2] Annulation of α-Purine-Substituted Acrylates with MBH Carbonates. , 2018, Organic Letters.

[14]  S. You,et al.  Palladium-Catalyzed Highly Stereoselective Dearomative [3 + 2] Cycloaddition of Nitrobenzofurans , 2017 .

[15]  Q. Peng,et al.  Highly Diastereo- and Enantioselective Palladium-Catalyzed [3 + 2] Cycloaddition of Vinyl Epoxides and α,β-Unsaturated Ketones. , 2015, Organic letters.

[16]  Yu Zhao,et al.  Stereoselective 1,6-Conjugate Addition/Annulation of para-Quinone Methides with Vinyl Epoxides/Cyclopropanes , 2016 .

[17]  Yao-Wei Gao,et al.  Synthesis of Azacyclic Nucleoside Analogues via Asymmetric [3 + 2] Cycloaddition of 9-(2-Tosylvinyl)-9H-purines. , 2016, Organic letters.

[18]  P. Herdewijn,et al.  Nucleosides with Transposed Base or 4'-Hydroxymethyl Moieties and Their Corresponding Oligonucleotides. , 2015, Chemical reviews.

[19]  Lei Yang,et al.  Pd-Catalyzed Asymmetric Decarboxylative Cycloaddition of Vinylethylene Carbonates with Imines. , 2015, Organic letters.

[20]  Yong Wang,et al.  A straightforward entry to chiral carbocyclic nucleoside analogues via the enantioselective [3+2] cycloaddition of α-nucleobase substituted acrylates. , 2015, Chemical communications.

[21]  Wanbin Zhang,et al.  Palladium-catalyzed enantioselective decarboxylative cycloaddition of vinylethylene carbonates with isocyanates. , 2015, Chemistry.

[22]  丁昌华,et al.  Highly Diastereo- and Enantioselective Palladium-Catalyzed [3+2] Cycloaddition of Vinyl Aziridines and alpha,beta-Unsaturated Ketones , 2015 .

[23]  Jing Xu,et al.  Palladium-catalyzed asymmetric decarboxylative cycloaddition of vinylethylene carbonates with Michael acceptors: construction of vicinal quaternary stereocenters. , 2014, Angewandte Chemie.

[24]  R. Schinazi,et al.  Synthesis of Nucleoside Phosphate and Phosphonate Prodrugs , 2014, Chemical reviews.

[25]  J. Waser,et al.  Synthesis of (carbo)nucleoside analogues by [3+2] annulation of aminocyclopropanes. , 2014, Angewandte Chemie.

[26]  Y. Kan,et al.  Palladium-catalyzed decarboxylative cycloaddition of vinylethylene carbonates with formaldehyde: enantioselective construction of tertiary vinylglycols. , 2014, Angewandte Chemie.

[27]  P. Chiu,et al.  Vinyl epoxides in organic synthesis. , 2014, Chemical reviews.

[28]  T. Ooi,et al.  Ligand-enabled multiple absolute stereocontrol in metal-catalysed cycloaddition for construction of contiguous all-carbon quaternary stereocentres , 2013, Nature Chemistry.

[29]  S. Castillón,et al.  Advances in the enantioselective synthesis of carbocyclic nucleosides. , 2013, Chemical Society reviews.

[30]  M. Shi,et al.  Palladium-Catalyzed Asymmetric Formal [3+2] Cycloaddition of Vinyl Cyclopropanes and β,γ-Unsaturated α-Keto Esters: An Effective Route to Highly Functionalized Cyclopentanes , 2012 .

[31]  Xiangqing Feng,et al.  Rhodium-catalyzed asymmetric formal cycloadditions of racemic butadiene monoxide with imines. , 2012, Organic letters.

[32]  Philip Chamberlain,et al.  Discovery of CC-930, an orally active anti-fibrotic JNK inhibitor. , 2012, Bioorganic & medicinal chemistry letters.

[33]  B. Trost,et al.  Palladium-catalyzed diastereo- and enantioselective synthesis of substituted cyclopentanes through a dynamic kinetic asymmetric formal [3+2]-cycloaddition of vinyl cyclopropanes and alkylidene azlactones. , 2011, Angewandte Chemie.

[34]  T. Kurahashi,et al.  Nickel-catalyzed [3 + 2] Cycloaddition of α,β-Unsaturated Ketones with Vinyl Oxiranes , 2011 .

[35]  Yoshinori Yamamoto,et al.  Formation of cyclic ethers via the palladium-catalyzed cycloaddition of activated olefins with allylic carbonates having a hydroxy group at the terminus of the carbon chain. , 2001, The Journal of organic chemistry.

[36]  Yoshinori Yamamoto,et al.  Palladium-Catalyzed Regioselective [3 + 2] Cycloaddition of Vinylic Oxiranes with Activated Olefins. A Facile Synthesis of Tetrahydrofuran Derivatives , 1998 .

[37]  T. Sells,et al.  Novel isomeric dideoxynucleosides as potential antiviral agents , 1994 .

[38]  S. Spergel,et al.  Synthesis and antiviral activity of novel isonucleoside analogs. , 1993, Journal of medicinal chemistry.

[39]  V. Nair,et al.  Isodideoxynucleosides : a conceptually new class of nucleoside antiviral agents , 1992 .

[40]  D. Huryn,et al.  Synthesis of iso-ddA, member of a novel class of anti-HIV agents , 1989 .