Organofluorine Chemistry: Electrophilic fluoroalkylation reagents and their reactions

Organometallics: transition metal-catalyzed reaction, mechanistic study including isolation of the key intermediate, kinetics

Material Science: living-polymerization of fluorinated monomer

1992-1996, Department of Environmental Science and Engineering, Nanjing University, China, Bachelor

1996-1999, Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Master

2000-2002, Chemistry Department, University of Massachusetts, Dartmouth, Master

2002-2007, Chemistry Department, Yale University, PhD

2010, Hundreds Talens Program of SIOC

2011, Pujiang Program of Shanghai

2013, Thieme Chemitry Journal Award

2015, Asia Core Program Lectureship Award

1.       Shao, X.-X.; Xu, C.-F; Lu, L.; Shen, Q.* “Shelf-Stable Electrophilic Reagents for Trifluoromethylthiolation” Acc. Chem. Res. 2015, 48, 1227

2.       Gu, Y.; Leng, X.-B.; Shen, Q.* “Cooperative Dual Palladium/Silver Catalyst for Direct Difluoromethylation of aryl Bromides and Iodides” Nat. Commun. 2014, 5, 5405, doi: 10.1038/ncomms6405

3.       Zhu, D.-H.; Gu, Y.; Lu, L.*; Shen, Q.* “N-Difluoromethylthiophthalimide: A Shelf-Stable Electrophilic Regent for Difluoromethylthiolation” J. Am. Chem. Soc. 2015, 137, 10547.

4.       Qi, Q.-Q.; Shen, Q.;^* Lu, L.^* “Copper-Mediated Aerobic Fluoroalkylation of Arylboronic Acids with Fluoroalkyl Iodides at Room Temperature” J. Am. Chem. Soc. 2012, 134, 6548

5.       Zhu, J.-S.; Liu, Y.-F.; Shen, Q.* “Direct of Difluoromethylation of Alcohols with an Electrophilic Difluoromethylated Sulfonium Ylide” Angew. Chem. Int. Ed. 2016, 55, 9050

6.       Wu, J.; Gu, Y.; Leng, X.-B.; Shen, Q.* “Copper-Promoted Sandmeyer Difluoromethylthiolation of Aryl and Heteroaryl Diazonium Salts” Angew. Chem. Int. Ed. 2015, 54, 7648

7.       Xu, C.-F.; Ma, B.-Q.; Shen, Q.* “N-Trifluoromethylthiosaccharin: An Easily Accessible, Shelf-Stable, Broadly Applicable Trifluoromethylthiolating Reagent”  Angew. Chem. Int. Ed. 2014, 53, 9316

8.       Hu, F.; Shao, X.-X.; Zu, D.-H.; Lu, L.; Shen, Q.* “Silver-Catalyzed Decarboxylative Trifluoromethylthiolation of Aliphatic Carboxylic Acids in Aqueous Emulsion” Angew. Chem. Int. Ed. 2014, 53, 6105.

9.       Wang, X.-Q.; Yang, T.; Cheng, X.-L.; Shen, Q.* “Enantioselective Electrophilic Trifluoromethylthiolation of b-Ketoesters: A Case of Reactivity and Selectivity Bias for Organocatalysis” Angew. Chem. Int. Ed. 2013, 52, 12860

10.    Shao, X.-X.; Wang, X.-Q.; Yang, T.; Lu, L.*; Shen, Q.* “An Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation” Angew. Chem. Int. Ed. 2013, 52, 3457

11.    Liu, T.; Shao, X.-X.; Wu, Y.-M.; Shen, Q.^* “Highly Selective Trifluoromethylation of 1,3-Disubstituted Arenes through Iridium-Catalyzed Arene Borylation” Angew. Chem. Int. Ed. 2012, 51, 540.

12.    Xu, C.-F.; Shen, Q.^* “Lewis Acid Mediated Trifluoromethylthio Lactonization/Lactamization” Org. Lett. 2015, 17, 4561

13.    Liu, Y.-F.; Shao, X.-X.; Lu, L.*; Shen, Q.^* “Trifluoromethyl-Substituted Sulfonium Ylide: Rh-Catalyzed Carbenoid Addition to Trifluoromethylthioether” Org. Lett. 2015, 17, 2752

14.    Xu, C.-F.; Shen, Q.^* “Palladium-Catalyzed Trifluoromethylthiolation of Aryl C−H Bonds” Org. Lett. 2014, 16, 2046

15.    Yu, D.-H.; Wang, C.-S.; Yao, C.; Shen, Q.;^* Lu, L.* “Nickel-Catalyzed α-Arylation of Zinc Enolates with Polyfluoroarenes via C–F Bond Activation under Neutral Conditions” Org. Lett. 2014, 16, 5544.

16.    Shao, X.-X.; Liu, T.-F.; Lu, L.;* Shen, Q.^* “Copper-Catalyzed Trifluoromethyl-thiolation of Primary and Secondary Alkylboronic Acids” Org. Lett. 2014, 16, 4738

17.    Yu, D.-H.; Lu, L.;* Shen, Q.^* “Palladium-Catalyzed Coupling of Polyfluorinated Arenes with Heteroarenes via C_F/C_H Activation” Org. Lett. 2013, 15, 940

18.    Liu, T.; Shen, Q.^* “Copper-Catalyzed Trifluoromethylation of Aryl and Vinyl Boronic Acids with An Electrophilic Trifluoromethylating Reagent” Org. Lett. 2011, 13, 2342.

19.    Wen, L.; Shen, Q.; Lu, L.^* “Enantioselective Organocatalytic Michael Addition of Aldehydes to Trifluoroethylidene Malonates” Org. Lett. 2010, 12, 4655.

20.    Shao, X.-X.; Xu, C.-F.; Lu, L.;* Shen, Q.^* “Structure−Reactivity Relationship of Trifluoromethanesulfenates: Discovery of an Electrophilic Trifluoromethylthiolating Reagent” J. Org. Chem. 2015, 80, 3012

21.    Hu, Z.-J.; Li, Y.-G.; Liu, K.; Shen, Q.^* “Bis(perfluoroalkyl) Phosphino-Oxazoline: A Modular, Stable, Strongly π-Accepting Ligand for Asymmetric Catalysis” J. Org. Chem. 2012, 77, 7957

22.    Xu, C.-F.; Chen, S.; Lu, L.;* Shen Q.^* “Preparation of Trifluorostyrenes via Palladium-Catalyzed Coupling of Aryl Boronic Acids with Chloro- and Bromo-Trifluoroethylene” J. Org. Chem. 2012, 77, 10314.

23.    Yu, D.-H.; Shen, Q.;^* Lu, L.^* “Selective Palladium-Catalyzed C−F Activation/Carbon−Carbon Bond Formation of Polyfluoroaryl Oxazolines”, J. Org. Chem. 2012, 77, 1798.

24.    Kang, K.; Xu, C.-F.; Shen Q.^* “Copper-catalyzed Trifluoromethylthiolation of Aryl and Vinyl Boronic Acids with a Shelf-Stable Electrophilic Trifluoromethylthiolating Reagent” Org. Chem. Front. 2014, 1, 294.

25.    Yang, T.; Long Lu, L.;* Shen Q.^* “Iron-mediated Markovnikov-selective hydro-trifluoromethylthiolation of unactivated alkenes” Chem. Commun. 2015, 51, 5479.

26.    Chang, D.-L.; Gu, Y.; Shen Q.^* “Pd-Catalyzed Difluoromethylation of Vinyl Bromides, Triflates, Tosylates and Nonaflates” Chem. Eur. J. 2015, 2015, 21, 6074

27.    Wen, L.-L.; Yin, L.; Shen, Q.;^* Lu, L.* “Enantioselective Organocatalytic Michael Addition of Nitroalkanes and Other Nucleophiles to β-Trifluoromethylated Acrylamides” ACS Catal. 2013, 3, 502

28.    Gu, Y.; Chang, D.-L.; Leng, X.-B.; Gu, Y.-C.; Shen Q.^{* “}Well-Defined, Shelf-Stable (NHC)Ag(CF₂H) Complexes for Difluoromethylation” Organometallics 2015, 34, 3065

29.    Lin, H.; Dong, X.-C.; Li, Y.-X.;^* Shen, Q.;^* Lu, L.^* “Highly Selective Activation of Vinyl C-S Bond over Aryl C-S Bond in Pd-Catalyzed Coupling of Trifluoromethyl-ated Vinyl Diphenyl Sulfonium Salts. A General Protocol to Trifluoromethylated Alkenes and Dienes” Eur. J. Org. Chem. 2012, 4675

30.    Liu, T.-F.; Shen, Q.^* “Progresses in Copper-mediated Formation of Trifluoromethylated Arene” Eur. J. Org. Chem. 2012, 6679

31.    Ma, B.-Q.; Shao, X.-X.; Shen, Q.^* “BrØsted Acid-Catalyzed Electrophilic Trifluoromethylthiolation of Indoles Using Thermally Stable Trifluoromethylthiolating Reagent” J. Fluorine Chem. 2015, 171, 73.

32.    Yang, T.; Shen, Q.;* Lu, L.* Chincona Alkaloid-Catalyzed Enantioselective Trifluoromethylthiolation of Oxindoles” Chin. J. Chem. 2014, 32, 678.

33.    Chen, S.; Xu, C.-F.; Lu, L.;* Shen, Q.* “Palladium-Catalyzed Cross-Coupling of Fluorinated Vinyl Chlorides with Terminal Alkynes: A General Protocol to Fluorinated Enynes” Chin. J. Chem. 2013, 31, 901

34.    Lu, C.-P.; Shen, Q.; Liu, D.^* “Transition Metal-Catalyzed Arene Trifluoromethylation” Youji Huaxue 2012, 32, 1380-1387.

35.    Liu, T.; Shen, Q.* “Copper-Catalyzed Trifluoromethylation of Aryl and Vinyl Boronic Acids with An Electrophilic Trifluoromethylating Reagent” Org. Lett. 2011, 13, 2342

36.    Lin, H.; Shen, Q.; Lu, L. “(β-Trifluoromethyl)Vinyl Sulfonium Salts: Preparation and Reactions with Active Methylene and Methenyl Compounds” J. Org. Chem. 2011, 76, 7359

37.    Wen, L.; Shen, Q.; Wan, X.; Lu, L. “Enantioselective Friedel-Crafts Alkylation of Indoles with Trifluoroethylidene Malonates by Copper-Bis(Oxazoline) Complexes: Construction of Trifluoromethyl-Substituted Stereogenic Tertiary Carbon Center” J. Org. Chem. 2011, 76, 2282

38.    Zhang, H.; Shen, Q.; Lu, L. “Highly Diastereoselective Synthesis of Optically Pure Trifluoromethyl-Substituted Imidazolidine, Oxazolidine and Thiazolidine” Tetrahedron Lett. 2011, 52, 349

39.    Wen, L.; Shen, Q.;  Lu, L. “The Recent Development of Organofluorine Chemistry in China: Asymmetric Construction of Stereogenic Trifluoromethyl-Substituted Carbon Center” Chimia 2011, 65, 894

40.    Qi, Q.; Shen, Q.; Lu, L. “Polyfluoroalkylation of 2-Aminothiazoles: Unexpected sp3 C-Cl Substitution Under Mild Conditions” Chinese J. Chem. 2011, 29, 2681

41.    Cruso, M. M.; Davis, D. A.; Shen, Q.; Odom, S. A.; Sottos, N. R.;^* White, S. W.;^* Moore, J. F.^* “Mechanically-Induced Chemical Changes in Polymeric Materials” Chem. Rev. 2009, 109, 5755-5798.

42.    Shen, Q.; Hartwig, J. F.^* “[(CyPF-^tBu)PdCl₂]: An Air-Stable, One-Component, Highly Efficient Catalyst for Amination of Heteroaryl and Aryl Halides” Org. Lett. 2008, 10, 4109-4112.

43.    Shen, Q.; Ogata, T.; Hartwig, J. F.^* “Highly Reactive, General and Long-Lived Catalysts for Palladium-Catalyzed Amination of Heteroaryl and Aryl Chlorides, Bromides, and Iodides: Scope and Structure–Activity Relationships” J. Am. Chem. Soc. 2008, 130, 6586-6596. (This paper was highlighted in Synfacts, 2008, 8, 859 as synfact of the month.)

44.    Shen, Q.; Hartwig, J. F.^* “Lewis Acid Acceleration of C-N Bond-Forming Reductive Elimination from Heteroaryl Palladium Complexes and Catalytic Amidation of Heteroaryl Bromides” J. Am. Chem. Soc. 2007, 129, 7734-7735.

45.    Shen, Q.; Hartwig, J. F.^* “Palladium-Catalyzed Coupling of Ammonia and Lithium Amide with Aryl Halides” J. Am. Chem. Soc. 2006, 128, 10028-10029. (This publication was listed as one of the most-accessed communications in J. Am. Chem. Soc. for the July-September 2006 period. This paper was also featured in C&E News, 2006, 84, 32. In addition, this paper was highlighted in Angew. Chem. Int. Ed. 2007, 46, 3402-3404.)

46.    Fernández-Rodríguez, M. A.; Shen, Q.; and Hartwig, J. F.^* “Highly Efficient and Functional-Group-Tolerant Catalysts for the Palladium-Catalyzed Coupling of Aryl Chlorides with Thiols” Chem. Eur. J. 2006, 12, 7582-7596.

47.    Fernández-Rodríguez, M. A.; Shen, Q.; and Hartwig, J. F.^* “A General and Long-Lived Catalyst for the Palladium-Catalyzed Coupling of Aryl Halides with Thiols” J. Am. Chem. Soc. 2006, 128, 2180-2181.

48.    Shen, Q.; Shekhar, S.; Stambuli, J. P.; Hartwig, J. F.^* “Highly Reactive, General, and Long-Lived Catalysts for Coupling Heteroaryl and Aryl Chlorides with Primary Nitrogen Nucleophiles”, Angew. Chem. Int. Ed. 2005, 44, 1371-1375.

49.    Shen Q.; Hammond, G. B.^* “Regiospecific Synthesis of Bicyclo- and Heterobicyclo- gem-Difluorocyclobutenes Using Functionalized Fluoroallenes and a Novel Mo-Catalyzed Intramolecular [2 + 2] Cycloaddition Reaction” J. Am. Chem. Soc. 2002, 124, 6534-6535.

50.    Shen, Q.; Chen, C.; Hammond, G. B.^* “Synthesis and X-ray Information of Substituted gem-Difluoroallenyl Amines”, J. Fluorine Chem. 2002, 117, 131-135.

51.    Shen Q.; Hammond, G. B.^* “Highly Efficient Synthesis of 1,1-Difluoro -2-substituted-1, 3-dienes and Dienynes from gem-Difluorohomoallenyl Bromide via Palladium-Catalyzed Cross-Coupling Reaction”, Org. Lett. 2001, 3, 2213-2215.

已指导学生

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